Académique Documents
Professionnel Documents
Culture Documents
MATERIALS FOR
ELECTRICAL ENGINEERING
Chosen chapters
Jaromír Drápala
Ostrava 2014
CONTENT
1. CONDUCTIVE MATERIALS 4
1.1 Highly conductive materials for electrical engineering 4
1.1.1 Copper 5
1.1.2 Copper alloys 7
1.1.2.1 Copper-zinc alloys 7
1.1.2.2 Copper tin alloys 8
1.1.2.3 Special copper alloys 11
1.1.3 Aluminum 12
1.1.3.1 Aluminum alloys 13
1.1.4 Noble metals – Ag, Au, Ru, Rh, Pd, Os, Ir, Pt 16
1.2 Materials for contacts 17
1.2.1 Requirements 17
1.2.2 Materials used for contacts 18
3. SUPERCONDUCTORS 45
3.1Examples of superconductor Applications 46
3.2Theory of superconductivity 47
3.3Low-temperature superconductive materials 49
3.4High-temperature superconductors 51
4. MAGNETIC MATERIALS 55
4.1Physical principle of magnetism 55
4.2Magnetic materials - properties 55
4.3Ferromagnetic materials 58
4.4Classification of magnetic materials 59
4.4.1 Magnetic soft materials 60
4.4.2 Magnetic metallic glass 62
4.4.3 Hard magnetic materials 64
4.5Oxide magnetic materials 69
8. INSULATORS 134
8.1Attributes of insulators and dielectrics 134
8.2Polarization of dielectrics and their properties 134
8.3Gaseous insulators 138
8.4Liquid insulators 140
8.5Solid insulators 141
8.5.1 Solid inorganic insulators 141
8.5.2 Solid organic insulators 144
8.6Dielectrics and capacitors 149
LITERATURE 151
1.1.1 COPPER - Cu
Copper properties
Copper is reddish metal with good hot and cold-formability. It has an excellent electrical and thermal
conductivity – Table 1.1. These properties however deteriorate quickly with impurities content. The impurities, for
example Fe, Si, P, O (in form of Cu 2O) strongly affect the conductivity of copper – Fig. 1.1. Copper is highly
corrosion resistant in atmospheric environment, it has good solderability at both high and low-temperature and is
part of many soldering alloys. It has relatively good weldability , problems are caused by its high thermal
conductivity. These properties are also common for copper alloys. Copper is easily degassed and is therefore
suitable construction material for electro-vacuum equipments. It has favorable mechanical properties, good
o
machinability (forming, cutting) . Its low melting point needs to be taken into account. Over 300 C (lower limit of
recrystallization) copper softens and loses its mechanical strength. For its high thermal expansivity it is not suitable
for glass-to-metal seals.
Another disadvantage of copper is its brittleness caused by annealing in hydrogen atmosphere. However this is
necessary for production of electro-vacuum parts; degassing after annealing is therefore necessary. This
embrittlement of copper is generally called hydrogen disease (Cu2O + H2 → 2 Cu + H2O).
Table 1.1 Relative electrical and thermal conductivity of technically pure copper (20 °C)
Relative electrical Relative thermal 110 Ag
Cd
Metal
Relativeel.conductivity[%]poměrnáel.ivost[%]
Ca
Ag 106 108
80 Zn
Cu 100 100
Sn
Au 72 76 70
Mg
Al 65 56 60
Ni
Mg 39 41 50 Al
Zn 29 29 40
Be
As
Fe 17 19
Sn 15 17 0 0.1 0.2 0.3 0.4 0.5 Fe
Si
Pb 8 9 Content of impurities [wt. %] P
Ti 4 4 koncentrace přísad [hm. %]
Table 1.2 lists the basic types of copper for electrical engineering applications (conductive materials), thermal
application, mechanical engineering, vacuum equipments etc.
Copper with reduced oxygen content - labeled Cu OFHC (Oxygen Free High Conductivity)
Reduced oxygen content is achieved by melting and casting in vacuum or protective atmosphere. Oxygen content is
held under 0.003 %. This material does not suffer from the hydrogen disease and is utilized in magnetrones and in
cathode X-ray tubes.
In electrical engineering, copper is used for electric power distribution in overhead wires and as conductive
core of cables and conductors. With regard to the copper prices increase, it is often replaced by aluminum. Copper
is the preferred choice for wire and foil conductor (the plates of the printed board circuit) production. However, in
microelectronics the wires are usually made of gold or AlSi alloy. Copper is also frequently used in alloys for
contact production.
Copper semi-finished products for electrical engineering are usually fabricated from cathodes of
electrolytically refined copper. For production of power cables, electrode copper (ECu) is preferred; primary
properties are high electrical conductivity and simplicity of fabrication. Parts used in electro vacuum industry are
fabricated from copper with reduced oxygen content. It is produced by melting and casting in vacuum or protective
atmosphere. This material does not become brittle in hydrogen atmosphere – does not suffer from the „hydrogen
disease“.
Copper wires for wire conductors and cables with rubber insulation are tin-coated – this hinders the corrosive
effect of sulfur which added to rubber as a vulcanizing agent. For contacts in high power hybrid integrated circuits,
the micro wires coated with aluminum are used. Copper core constitutes the thermal and electrical conductor and
the aluminum cover functions as the connection agent.
Fig. 1.2 Copper – zinc binary phase diagram (by Massalski, 1998)
Classification of brasses:
a) Brasses for forming contain from 5 to 42 wt. % Zn and can be both homogenous and heterogenous. They are
labeled with the Ms label with added number which states the copper content. They are fabricated as semi-
finished products (strips, sheets, rods, wires, tubes) and in soft (annealed), medium, rigid or spring-rigid state.
Tombac (pinchbeck) is Cu-Zn alloys with copper content higher than 80 wt. % Cu (Ms 96 to Ms 80). These alloys
have good resistance against atmospheric corrosion and good low temperature formability. They are mostly
produced in form of strips and sheets for pressing, drawing and minting. They are used as components for
electrical engineering, for pressure gauges, corrugated tubes, membranes, sieves. Other use: coins, plaques.
Single-phase brasses α brasses are mostly utilized in the form of sheets, strips or wires. Their strength and
ductility increases with zinc content; the brasses Ms 70 and Ms 67 have optimal cold working properties.
Two-phase brasses α+β' brasses form when the solubility limit of zinc in copper solid solution is exceeded. Most
common alloys are Ms 63, Ms 60 and Ms 58 for forgings. Addition of 1 ÷ 2 wt. % Pb enhances their machinability.
The disadvantage of two-phase brasses is their tendency to stress-corrosion cracking, also called “seasonal
cracking”. Internally stressed parts, exposed to corrosive environment, especially ammonium, can crack even
without external load, e.g. during storage. To remove the internal stress, given parts needs to be annealed at 250 to
350 oC.
b) Brasses for casting commonly contain between 58 and 63 wt. % Cu. Their structure is heterogeneous α+β'.
They typically have good fluidity and low tendency to segregation. Their machinability can be enhanced by lead
addition (1 ÷ 3 wt. %).
Certain types of brasses with melting point over 500 oC belong to the group of so called hard solders (brazing
metals), used for metal parts joining.
The brass hard solders with silver are more expensive, have lower melting points and if the content of silver
exceeds 50 wt. %, they are reffered to as silver alloys or silver solders.
Bronze is alloy of copper and tin or other elements. Bronzes are generally copper alloys with the exception of
brasses. Bronze type is therefore labeled according to its main alloying element (e.g. tin bronze, aluminum bronze,
lead bronze, nickel bronze, manganese bronze). Bronze is used in all applications requiring higher tensile strength
Rm and corrosion resistance than brasses can achieve.
The oldest bronze type is the tin bronze. Equilibrium binary diagram copper-tin (see Fig. 1.3) shows large
number of phases. At room temperature, (36.5 ÷ 38 wt. % Sn) and ’ (~ 61 wt. % Sn) phases are stable. , a phases
are stable at higher temperatures. The Cu-Sn alloy does not reach equilibrium structure at normal cooling rates. The
reason for this is the strong segregation of tin during bronze solidification and very slow diffusion of tin at low
temperatures.
Special bronzes
Tin in special bronzes is partially or completely replaced by other elements which are also used to differentiate the
kind. Based on their structure and related properties and also by the manufacturing process, they are divided in two
different groups – bronzes for forming and bronzes for casting.
Red bronzes
are ternary Cu-Sn-Zn alloys. Some are also alloyed with low amounts of lead. They have good machinability and
their surface can be easily polished. These are cheaper, thanks to the lower content of tin, compared to the binary
Cu-Sn bronzes. Common application includes armatures casts, pump parts etc. They have similar composition as
bronzes for sculptures – the content of zinc is often much higher than tin content.
Aluminum bronzes
are Cu-Al alloys, possibly with another metal. They contain up to 12 wt. % Al. Bronzes with higher Al content
suffer from unfavorable brittleness. Aluminum bronzes are characteristic for their good heat resistance up to 800 °C
and high corrosion and fatigue resistance (even corrosion fatigue). They are also very hard, have high abrasion
resistance and good sliding properties. This material is suitable for memorial tablets, welding jaws, furnace electric
contact clamps worm wheels, armatures, valve seats, ball bearing for high pressure and slow speed applications.
Silicon bronzes
They are used as a replacement for costly tin bronzes. Cu + Si alloys (usually 3 to 4 % Si) have better mechanical
properties than tin bronzes and also good fluidity. Primary crystallization occurs in wide temperature range
segregation tendency, non-equilibrium crystallization (rapid cooling) heterogenous structure. Good high and low
formability used for drawing and minting. These alloys have higher strength and can be used in wider temperature
range (-180 up to +200 °C). The hardness and strength can be improved by manganese, nickel or zinc. Relatively
bad machinability can be enhanced by lead (0.5 wt. % Pb). Alloys for forming contain up to 3.5 wt. % Si, the alloys
for casting up to 5 wt. % Si.
Phosphor bronze
Alloy CuP8 is used for brazing. The structure is eutectic and the alloy has an excellent fluidity. However, the solder
joints are brittle and cannot be used to brazing of steels or any mechanically strained parts, especially with dynamic
loading.
Beryllium bronze
belongs to the group of thermally hardenable copper alloys and it can reach the highest strength of all copper
materials. Addition of beryllium is around 1 - 2 wt. . 2 wt. % is an optimum which, after thermal hardening, can
provide ultimate tensile strength of 1400 MPa and 400 HV hardness. Beryllium bronzes exhibit excellent spring
properties, best outside the non-ferrous alloys group. They maintain their high tensile strength even after
prolonged high-temperature exposure.
Beryllium bronze foils. Beryllium bronze can be rolled to very thin foils – up to 1.4 m while maintaining
reasonable strength. It is often used as nonmagnetic insulation in recording heads for media recording.
Beryllium bronzes with addition of Ni, Co, Mn, Ti. They have (apart from excellent mechanical properties) a good
corrosion resistance. These alloys are used for production of springs with good electric conductivity, non-
sparking tools for mining applications and chemical industry, swaging for forming, ball bearings for large loads
and high radial speeds (superb friction properties).
Note: The content (concentration) of alloying elements will be in the next text used only in % (it means in wt. %).
B. Manganese bronze
Manganin (86 % Cu, 12 % Mn, 2 % Ni) . Its properties are not stable and the alloy is therefore thermally aged at
elevated temperatures in several cycles. Ultimate tensile strength reaches 500 ÷ 550 MPa. Maximal operation
temperature is 140 °C. Manganin is, as resistive material, used for production of stable and precise resistors
produced from wires or sheets (manganin foil is glued on laminated paper from both sides and subsequently
etched). Another use is manufacture of resistive pressure gauges which make use of the piezoelectric effect –
changes in pressure are detected by changes in electrical resistance of the bronze.
Zeranin (87 % Cu, 7 % Mn). Very similar properties to managanin, but can also contain germanium. Tensile
strength is of 350 ÷ 400 MPa. Used for production of resistors with high accuracy.
Cast and formed alloys – complex alloys with low concentrations of Ni, Si, Be, Al, Cr, Zr, Co, V, Fe.
Application: welding electrodes, thermally stressed aircraft parts.
Beryllium bronzes (2 ÷ 2.5 % Be), typically processed by water quenching from 800 °C, tempering at 250 to 350
°C, 2 to 3 hours. They have about 55 % electrical conductivity of Cu. ↑ R m, ↑ electrical conductivity.
Application: heavily strained springs with electrical current flowing through them.
Electrical conductive bronzes: ~ 1.2 ÷ 1.5 % Sn 40 ÷ 50 % electrical conductivity of Cu. Rm ~ 600 ÷ 700 MPa.
Cu + 0.5 ÷ 1.5 % Cd. Application: very long-distance conduction, trolley wires, welding electrodes.
Cu + ~ 0.1 % Ag. Decreased conductivity by 0.7 % compared to pure Cu, ↑ recrystallization temperature (300 °C).
Application: rotor wiring in turbo alternators.
Cu + 0.5 ÷ 1 % Cr. Application: electrodes in resistance welding devices.
Cu + 0.3 ÷ 1 % Te. Good machinability, ↑ el. conductivity.
1.1.3 ALUMINUM - Al
Development in production of high-purity aluminum allowed utilization of its good electrical conductivity
which is about 65 % of copper. Aluminum is therefore amongst the top four metals with lowest electrical
resistance preceded by silver, gold and copper. Important areas of application are electrical engineering and
microelectronics. Aluminum is commonly used for fabrication of wires (external conductors, wiring, cables) and
micro-wires, its good formability at normal temperatures allows the production of various parts and casings
(saddle washers). Dielectric properties of its oxides forming on the surface are utilized in production of electrolytic
capacitors. Aluminum is often used as and coating materials, since the coating layers are easily produced by vapor
deposition or sputtering, the coatings are also used as and reflector in black-and-white or color TV screen and as
conductive surface in microelectronic parts, for cast parts – coolers etc.
Advantages Al is ~ 3 times lighter than Cu; Al cable with the same electrical resistance weighs about half of the Cu
cable; good corrosion resistance.
Disadvantages low strength (the aluminum external conductor network needs to be combined with steel suspension
ropes).
Alloying and forming cannot be used to improve its strength => lowers the electrical conductivity, low
crystallization temperatures.
Power cables
PVC insulated cables – cables with aluminum core, PVC insulation and wire braiding.
Aluminum wire braids – used for overhead high voltage cables.
Aluminum strips – for distribution network connection.
Steel- aluminum conductors for exterior, high-voltage use have steel core surrounded by aluminum cover. The
steel has tensile strength of 1200 MPa to ensure necessary mechanical strength, aluminum provides good electrical
conductivity.
Thin cables and micro-cables
Electro-conducting aluminum 99.5 % is not sufficiently pure for connection of microelectronic components.
Therefore the 99.99 % pure aluminum is used. Because of its low strength, the minimum diameter is 0.2 mm.
Lower diameter wires can be produced only from aluminum alloyed with silicon, magnesium or copper.
Aluminum foils for electrolytic capacitors
They are used for production of electrolytic capacitors as anode and cathode foils. Higher specific surface and
therefore higher capacity is achieved by chemical or electrochemical etching, nowadays in mixture of common salt
and other compounds. Dielectric layer composes of aluminum oxide prepared by anodic oxidation of etched anodic
foil.
2. Al – Ni alloys are mostly used for poly-component systems operated at elevated temperatures.
Ni (up to ~ 2.5 %) in some alloys enhances mechanical properties at normal and elevated temperatures and also
improves corrosion resistance.
3. Al – Zn alloys have high strength, lower toughness, lower corrosion resistance and are more easily hot-formed.
4. Al – Mg alloys. Mg is added to most of the Al alloys. It enhances its hardening properties, increases corrosion
resistance. Mg content in alloys for forming is up to do 8 %; in the alloys for casting it is up to 11 %.
5. Al – Mg – Mn alloys have high strength, are plastic, easy to drawn, have good corrosion resistance. Mn
enhances the hardening and has no significant effect on the structure.
6. Duralumin (dural) – thermally hardenable aluminum alloy Al-Cu-Mg-Mn with 4 % Cu, 0.6 % Mg and 0.6 %
Mn. Hardened alloys have tensile strength Rm = 450 to 550 MPa. They are used for production of formed semi-
finished products. Alloy with higher magnesium (about 1.2 1.6 %) and manganese content ( 1 %).
Super-duralumin – has even higher tensile strength (more than 550 MPa). Duralumin alloys are used in wide
range of construction applications.
7. Aldrey alloy – aluminum alloy for electro-conducting. The alloys consists of Al, 0.5 % Si and 0.5 % Mg. It has
about double the tensile strengths of pure aluminum while keeping its good electrical conductivity. Thermal
treatment and low-temperature forming enhances the tensile strength up to 300 MPa which is sufficient for
production of high-voltage power conductors.
8. Jereal alloy – with increased (by about 0.15 %) content of Zn. Thermally treated wires reach strength of 360
MPa. Jereal can be used for exterior network cables and also for applications bellow 80 °C. Recrystallization
caused by higher temperatures deteriorates its mechanical properties.
9. Condal alloy is aluminum alloy with 0.4 % Mg and 0.4 % Fe. It is suitable for transformer wiring, electrical
rotary devices and any other applications where pure aluminum cannot be used due to limited mechanical
properties.
10. Al – Ni alloy was a big achievement in the development of magnetically hard materials. It is alloyed with Fe,
Al, Ni and has unusually viable magnetic properties. With the aluminum content of 12 to 14 %, 24 to 28 % Ni,
3
(balance Fe) is the maximum energy product (BH)max = 5300 J/m while Br = 0,55 to 0,65 T and Hc = 40000 to
51000 A/m. To achieve such properties, the alloy needs to be thermally worked, rapidly cooled from 1200 to 600
°C, held at this temperature for several hours and then slowly cooled. Addition of cobalt, copper or titanium and
cooling of the material in strong magnetic field can further enhance the properties of Al – Ni alloys. In such case,
the correct label of the alloy is Al – Ni – Co (apart from Fe, the most important alloying elements are Al, Ni, Co
which are the typical hard-ferromagnetic materials). Optimal properties are reached at 8 % Al, 14 % Ni, 24 % Co, 3
% Cu and balance of Fe. Thermal treatment consists of rapid cooling (quenching) from 1300 °C (from 900 °C in
strong magnetic field) and hardening at around 600 °C. After this treatment, the alloy has Br = 1 to 1.4 T, Hc =
40000 to 52000 A/m and (BH)max = 15000 to 22000 J/m3. The only disadvantage of Alnico magnets is their
brittleness caused by their stiffness which makes the machining complicated. This is also true for Al – Ni alloys.
Low machinability along with low dimensional accuracy and brittleness of cast magnets forced the magnet
manufacturers to look for different technology – powder metallurgy. Metal powders prepared by grinding are
pressed into desired shape and annealed at 1300 °C. Alni and Alnico magnets produced by this process have
magnetic properties comparable to the cast material but also have higher strength, are not brittle and have better
machinability. The application range is very wide, 80 % of all hard ferromagnetic materials is used for permanent
magnets.
Al powder metallurgy
Sintered Aluminum Powder is special product used for production of pressed, rolled, forged and other sintered
semi-finished products from both pure aluminum and its alloys.
Aluminum conductors
The term „aluminum conductors for electrical engineering” is used for production of conductors with aluminum
core which must fulfil requirements given by both standards and operation demands. Important attributes of
aluminum wires are: outer diameter, tensile strength, ductility, bend fatigue resistance and electrical resistance. 99.5
% aluminum (EAl 99.5) is the precursor for conductor production. Main impurities are Fe, Si, Cu, Mn, Mg, Zn.
Al wire production technology:
Aluminum wire can be produced by three different technologies:
a) Rolling.
b) Pressing.
c) Continual forming of rolled wire at elevated temperature.
Cold wire drawing of aluminum and its alloys
Aluminum wires drawn at normal temperature are produced from both pure aluminum and its alloys. Wire
product categories are: round wired with normal precision, precise round wires, rivet round wires, square and
hexagonal wires. Wires rolled at elevated temperature or extruded wires are the precursors for the cold-formed
aluminum wires.
Aluminum cables production
AlFe cables are used as the exterior overhead distribution network. AlFe cables consist of steel core wire or
rope with 1 to 4 layers of outer shell from aluminum wire. For example: the exterior 220 kV high-voltage
distribution network uses AlFe 450/52 rope (i.e. approximately: Al = 450 mm 2, Fe = 52 mm2).
Aluminum wires for distribution network are divided in two groups; common aluminum cables and aluminum
cables with steel core – Fig. 1.4. Common aluminum cables are fabricated from 1.7 to 3.55 mm diameter wire
with one up to three layers – on cable therefore consist of 7, 9 and 37 wires. Aluminum cables with steel core
have the Al:Fe ratio of 3:1, 4:1, 6:1 and 8:1. Steel core can consist of one, three, seven, twelve and nineteen wires.
Number of aluminum wires is between six and fifty-two. Wires are reeled in four
layers around the steel core. The steel core in steel-aluminum cables can be also
reeled around the base steel thread.
1.1.4 NOBLE METALS – Ag, Au, Ru, Rh, Pd, Os, Ir, Pt
Noble metals are gold, silver, platinum group metals and their alloys. (Table 1.5). Electrical engineering and
electro-technical industry consumes about 40 % of their production. There are microelectronic components labeled
as „without noble metals” but yet still usually utilize golden micro-wires although the golden solder and gold
coating have been largely replaced with other materials.
Gold has the highest corrosion resistance in atmospheric conditions. It does not react with oxygen. Therefore is
used as protective coating on other metals in electronics. Gold is immune even in melted state, wets other metals
which makes it perfect soldering material. It also wets silicon. It is difficult to replace gold solder in demanding
applications. Its lower melting temperature is sometimes problematic during production of contacts – this
sometimes leads to sticking of the contacts during its operation. Platinum is therefore more suitable in some
applications, however its ability to catalyze organic compounds resulting in non-conductive layer on its surface
restricts its use in other applications. Noble metals are characteristic for their stability in air and chemical
resistance. Each noble metal has its unique properties, utilized in electro-technical components.
Silver and its alloys are widely used in electrical engineering industry. It is being used for its high thermal and
electrical conductivity and the problems with surface forming sulfides have been overcome. The palladium is,
thanks for its relatively low price, used more frequently. Noble-metals coatings on joints often react with the base
metal forming intermetallic compounds with disadvantageous properties. Some noble metals are, in form of
powders, used as conducting powders production for thick-layer applications.
1.2.1 Requirements
Materials for electrical contacts are required to have specific electrical, mechanical and thermal properties. No
electrical contact can transport electricity without dissipation. Unwanted phenomena, such as warming of the
material, transport of the material and oxidation, often occur in contacts during current transport. From the material
point of view, the highest demands come from switching the power circuits during operation. Material requirements
in this case are toughness and spring toughness. Bimetals are produced in form of strips, wires and profiles.
Phenomena occurring during the contact operation need to be taken into account when choice the correct material:
1. Low and stable contact resistance – contact resistance needs to be small and stable during the whole lifetime of
the component. These requirements are mostly met by the noble metals and their alloys. Materials need to be
resistant in air, vapors, and oil; low oxidation noble metals, carbon.
2. Good electrical and thermal conductivity Cu , Ag
Ag Rm, HB Ag + Cu are more viable
Ag + 3.5Cu service like, HB, I , U
Application: medium switching throughput, cam switches, mechanically stressed contacts.
Powder metallurgy is preferred over melting and casting decrease in el. conductivity.
Material types: AgNi , WCu , WAg Cu , Ag 20÷40 so called pseudo-alloys.
Production of pseudo-alloys: diffusion, capillary forces, infiltration saturation by liquid metal .
Sintered carbides WC + 6 % Co hardness, abrasion resistance (contacts for telephone relays (enhanced by
addition of 1 2 % Os)).
3. Low burn-off, arcing resistance. Higher throughput contacts are commonly spark eroded. The cause for this is
melting, transport of the metal by sputtering or evaporation which takes place at high loads when an arc occurs.
Their lifetime is predominantly determined by arcing (during the circuit switching off) which needs to be
prevented. This can be resolved by proper material choice, or the circuit design, e.g. use of arc extinguishing
circuit breakers (addition of capacitor with resistor, diode or resistor parallel to contact or inductance). The
A. PURE METALS
Pure silver – silver is the most frequently employed material for contacts due to its excellent electrical and
thermal conductivity and high resistance against oxidation.
Its main disadvantages are:
Pure gold is the most noble metal with excellent electrical and thermal conductivity. Gold is immune to corrosion.
It is stable even in polluted atmosphere and unlike platinum group metals does not catalyze organic compounds.
These properties are also typical for gold alloys which can overcome the disadvantages of pure gold, such as:
low abrasive resistance, low melting point and also tendency to material migration and contact welding.
It is suitable for low throughput contacts with low friction forces, high switching rate and the allowable
throughput is several milliamperes.
Copper is commonly used for low-cost contacts with high switching rate (non-conductive oxide forming on the
surface is removed by the switching of the circuit). Commercially it is available in semi-hard or hard form.
Platinum group metal materials – contact parts are fabricated from platinum, palladium and iridium. All metals
from platinum group have one major disadvantage – formation of polymer layer on the contact surface. This is
most notable on Pd, followed by platinum.
Platinum has high chemical resistance, does not form oxide layer. Apart from good mechanical properties it is also
abrasive resistant. Low burn-off rate is ensured by its high melting point. Disadvantages are lower electrical and
thermal conductivity and high cost.
Palladium has very similar properties to platinum, but it is much cheaper. Disadvantage is its low oxidation
resistance between 400 800 °C. Typical application involves relay electronics in the form of rivet and desk
contacts.
Mercury is suitable for contacts with low switching rate due to its very low contact resistance. Mercury contacts
are nowadays being replaced by solid state power switches (human health issues).
Tungsten and molybdenum have high melting points and hardness also as resistance against the arc damage. It is
suitable for high-throughput, abrasion, burn-off and welding resistant contacts. Used for high-voltage switches,
relay switches etc.
Graphite – non-metallic material suitable for moving contacts in radial-operation devices and electric motors.
Graphite brushes provide contact between immobile (stator) and moving part (rotor) of the machine. The
brushes are fabricated from hard graphite, natural graphite, electro-graphite and metal- graphite. Brushes from
hard graphite have relatively high resistivity toughness and hardness. Natural graphite brushes are soft, have
good electrical conductivity and can withstand high centrifugal forces. Electro- graphite brushes have good
toughness. They have a good electrical conductivity, resist to high radial velocities and high current throughput.
Typically employed in large DC mining and rolling machines, commutator machines etc. Metal-graphite
brushes have relatively low resistivity and are used in machines with lower operating voltage and high current
levels. Brushes with higher copper content can be operated at higher currents, but lower radial velocities. Major
advantage of graphite contact is that they don’t suffer from burn-off and do not weld – carbon does not melt in
arc. Although some of the carbon oxidation takes place producing gaseous CO2 during arc extinguishing, the
newly-formed graphite surface remains clean.
B. ALLOY MATERIALS
i
i
v
s Constantan has not only high specific electrical resistance, but
.
t 40
i
s
also low thermal coefficient of electrical resistance. High
[
e
r 30 thermoelectric voltage relatively to copper however prevents
resistivity
Cu-Ni-Al (Cu Ni6 Al1) – high oxidation and high-temperature resistance. Cast and formed alloys: complex alloys
with low amounts of Ni, Si, Be, Al, Cr, Co, V, Fe (application: weld electrodes, thermally stressed aircraft
components etc.).
4. Nickelin is a nickel bronze (30 % Ni) with 3 % of manganese. Used for fabrication of resistor which are not
required to have stable resistance – regulation and switching purposes (technical rheostats, regulation resistors).
Oxide layer can be prepared by annealing in oxidation atmosphere. This layer has sufficient resistance to
facilitate an insulator for common use.
5. Isotan is used for common resistors production.
6. Isaohm, nicrothal, stabilohm are resistive Cr- Ni alloys. They have relatively high specific resistivity of around
1.3 ·m. Used for precise resistors with high resistance wiring.
7. Au-Cr alloy – gold content is higher than chromium content. Maintaining the content of chromium at 2.05
% has significant effect, especially on thermal coefficient of electrical resistance R. This material is used for
production of precise resistors and resistance standards. Alternatives with lower cost are preferred. Au with 2 %
Cr alloy annealed for several days in vacuum is completely stable at 150 °C. Its electrical resistance is
temperature independent in wide temperature range. However, it is strongly affected by mechanical strain in the
structure, for example occurring during humidity level changes. To assure precise measurement, these standards
are set in argon filled casing.
8. Cast iron has specific resistivity of 0.7 ·m and highest allowable operation temperature of 500 °C. It is used for
manufacture of planar segments for power switches.
10. Nimonic 80A (73.1 % Ni; 19.4 % Cr; 2.5 % Ti; 1.3 % Al; 1.1 % Co; 0.74 % Si; 0.6 % Fe; 0.25 % Mn; 0.1
% C) – withstands high loads, 3 times higher resistivity than manganin, suitable to use in temperatures up to 100
°C.
11. Ag alloys e.g. 91 % Ag + 9 % Mn for precise resistors, 78 85 % Ag + 8 17 % Mn + 3 9 % Sn for common
resistors. Very low thermal coefficient of electrical resistance R
12. Mn –Ni–Cu alloys have the highest thermal coefficient of el. resistance of all mentioned alloys, roughly 5
times greater than manganin. Apart from that, also exhibit low thermo-electrical voltage, are malleable. Can be
drawn into very thin wires.
13. Ni–Cr–Al alloys have 3 times the specific resistance of manganin and lower thermal coefficient of electrical
resistance. Their resistance is less temperature dependent in the –55 to +100 °C range than manganin. The thermal
-1
coefficient can be further lowered by suitable thermal treatment to –0.0005 K . Their resistance doesn’t change
during operation exposure. These alloys can be drawn to very thin wires (10÷15 µm diameter). These alloys enabled
miniaturization of resistors. Another advantage is their resistance against surface oxidation at elevated temperature.
Soldering is complicated due to formation of chromium oxides, however these can be removed by correct soldering
technology.
1. Cr–Ni alloy contains 20 % of chromium and 80 % of nickel. It is called chromnickel. Specific resistivity
at 20 °C is 1.09 · m, 1.16 ·m at 1000 °C. Commercially available in form of wires with diameter of up to 0.01
mm and strips. It has very high thermal resistance – operation temperatures can go as high as 800 to 1200 °C.
Chromium oxide forming on the surface enhances the chemical and oxidation resistance as well as mechanical
shock resistance of the material. However high nickel content increases its price. Chromnickel is employed as
coil wiring of common resistors for electrical ovens and cookers. Compound thin-plate resistors are produced by
deposition of the alloy on ceramic (fosterite) plate.
2. Cr–Ni–Fe is based on chromium and nickel. Chromium content is about 20 % in all alloys of this group,
nickel content varies from 20 to 80 %. Nickel increases its specific resistivity – from 0.95 to 1.1 ·m as well as
the heat resistance of the alloys; their allowed operation temperature rises from 900 to 1200 °C. Alloys of this
group are labeled CN 20, CN 30, CN 60 and CN 80 (number indicates % of nickel content). Commercial names
are cekas , feronichrom, ferochronin. Cr– Ni–Fe are cheaper than Cr–Ni alloys, but with worse properties.
Increasing the iron content lowers the operation temperature and their oxidation resistance.
3. Fe–Cr- Al alloys usually contain 20 to 30 % of chromium, 3 to 6 % of aluminum and iron balance. Their
structure is ferritic; they are harder, more brittle and have lower formability compared to the Cr-Ni-Fe alloys.
Their specific resistivity is high: 1.25 to 1.45 ·m. Aluminum addition forms protective layer of aluminum oxide
on its surface which increases its allowable operation temperature up to 1350 °C. 2÷3 % of silicon has similar
effect. Domestic available Fe–Cr–Al alloys are labeled AC 20, AC 22, AC 30, where the number states the
chromium content in %, Fe–Cr–Si alloys with silicon are labeled SC 20 and so forth. Alloy “Canthal”, contains,
besides iron, chromium and aluminum, also 0.25 to 3 % of cobalt. It is being produced in various categories,
e.g. Canthal Al for use at up to 1350 °C, Canthal A (up to 1300 °C) and Canthal DS (up to 1150 °C). These
alloys are sometimes also called fechral and chromal. Temperature limit for Fe–Cr–Al is 1350 °C; they become
brittle and soft at higher temperature which significantly reduces its lifetime.
Requirements: high accuracy (mV/K), stable dependency of thermoelectric voltage, linear or approximately linear
dependence of U = f( T), good mechanical properties, chemical resistance, thermal resistance and long-term
stability of properties of the material.
Alloy types: Cu; Fe; Ni; Pt; 50 % Ni + 50 % Cr; 87.5 % Ni + 12.5 % Cr; 84 % Ni + 16 % Mo; 56 % Cu + 44 % Ni
(kopel); 90 % Ni + 10 % Cr (chromel); 95 % Ni + Al + Mn + Si (alumel); 90 % Pt + 10 % Rh; 94 % Pt + 6 %
Rh; 70 % Pt + 30 % Rh …
Application: temperature measurements and direct conversion of heat to electricity (some semiconductors).
Table 2.2 Chemical composition, mechanical properties and resistivity of some thermocouple materials for low and
medium temperature measurements
Chemical composition [wt. %] Mechanical properties Resistivity
Ni alloys Ni Fe Si Mn Cu Rm Cr HB Al [ .cm]
[MPa] [%]
Chromel (ch) balance 9÷10 60÷70 35÷45 150÷200 60÷70
Alumel (a) balance 0.85÷2 1.8÷2.2 1.8÷2.5 56 36 130 25÷35
Constantan (ko) 40 1.5 bal. 40÷50 30 80÷90 48
Kopel (k) 43 0.5 bal. 40 35 85÷90 49÷50
Nichrom Ch20N80 75÷78 bal. 20÷23 70 50 115
Nichrom Ch15N60 55÷61 bal. 15÷18 64 28÷30 180÷230 110
35
30 Chromel Copper
Electromotive force (ems) [mV]
25
20 Cr – Ni
15
10 Cu – Fe
5
0
-5 Alumel
-10
-15 Nickel Fig. 2.4 Temperature
-20
-25
Kopel
Constantan dependence of electromotive
-30 voltage of chosen metals,
-35 -200 0 200 400 600 800 1000 1200 1400 relative to platinum
Temperature [°C]
[mV]
J Fe-CuNi - 200 to 750
E NiCr-CuNi, ch-ko - 100 to 900
Fe-ko
Voltage
K Ni-CrNi, ch-a - 200 to 1200
N NiCrSi-NiSi - 200 to 1200
S PtRh10-Pt 0 to 1600
R PtRh13-Pt 0 to 1600 Cu-ko
-1 -1
The S [V·K ] is Seebeck coefficient (thermoelectric sensitivity), T [K] is thermodynamic temperature, [S·m ] is
electric conductivity and [W·m-1·K-1] is thermal conductivity.
Metals are usually poor thermoelectric materials since they exhibit low Seebeck coefficient and their high
thermal conductivity is mostly electron based. Insulators have high Seebeck coefficient and low electron
conductivity but also very low electric conductivity. Semiconductors are therefore the best material for thermo-
electrics, with their properties somewhere between metals and insulators.
Thermoelectric cooling employs the Peltier effect – thermal gradient occurs in materiel when subjected to
electric or magnetic field. Electric field causes electron in material to move in unified motion – this is basically an
energy transport which exhibits as current flowing from the positive to the negative terminal and thermal gradient
between the two terminals. Z sums up the essential properties of the thermocouple. Industrial thermocouples have
Z
-3 -1
= 1.5 ÷ 3·10 K , Z of laboratory thermocouples is usually higher. Table 2.4 shows the characteristics of some
semiconductor thermoelectric materials.
Thermoelectric converter resp. Peltier couple is power source converting the heat to electricity by Seebeck
U = UP + UN thermoelectric effect. Schema of thermoelectric converter setup is shown on Fig.
2.6. Thermoelectric converter consists of two different semiconductors – one is
P-type, the other is N-type. Semiconductors are joined at one end by a bridge
R I (heat Q1 input point) to the thermo-converter (hot contact, thermodynamic
temperature T1). The other side of the semiconductor has metallic contacts which
+ Q2 Q2 - work as cooling surfaces for removing the Q2 heat from the converter (cold
contact, thermodynamic temperature T2) and also facilitating the circuit contact
T2
terminals. Thermoelectric voltage is generated in the opened circuit and the
Semiconductor Semiconductor
output power is consumed by the connected resistor – Fig. 2.6. Efficiency and
UP P – type N – type UN output of the converter depends on the material (semiconductor), dimensions of
S, , S, , the semiconductor rods and the resistance R of the resistor. Material also
determines the maximum allowable temperature T1. The basic characteristic of
T1 the converter according to Fig. 2.6 are: diameter and length of the rod, resistivity
Q1 Q1 N, P, Seebeck coefficients SN, SP and thermal conductivities N, P.
Fig. 2.6 Principle of semiconductor conductor
Jaromír Drápala © Materials for electrical engineering 32
Thermoelectric converters can also directly convert heat to electricity. They are being employed as alternative
new-generation power sources to some extent, mostly as a part of systems, where internal heat flow with high
temperature gradient is present. These are suitable for long-term operation (tens of years, space travels or
cathodically attacked gas line protection).
Thermoelectric generator usually consists of P and N type semiconductor with temperature gradient between
them. These components are connected in series electrically and in parallel thermally. By connecting some kind of
appliance to the generator circuit, electrical power is produced. Combination of P and N-type semiconductor
generates the highest powers and voltages. The Seebeck coefficients for P and N-type semiconductor have opposite
signs – this effectively doubles the thermoelectric performance power – Fig. 2.6. For effective energy conversion,
high thermoelectric coefficients but also high electric and thermal conductivity ( , are necessary. Combined
characteristics of the thermoelectric conversion material are described by the Z efficiency factor.
The contact between metallic parts and semiconductors is crucial – the contact resistance must be low and it
also has to be stable at elevated temperatures. Voltage is adjusted by connecting multiple converters in series or
cascade with different semiconductor materials used along the temperature gradient (low-, medium-, high-
temperature).
Basic materials for Peltier couple are bismuth-tellurides i.e. ternary Bi -Te- Se systems (N-type) and Bi-Sb-Te
(P-type). These have good thermoelectric properties, low specific resistivity and low thermal conductivity.
Connecting bridges are usually made of copper (low resistivity, solderable). Its main drawback is the possibility of
diffusion towards semiconductor material thus worsening its properties. Contact between the bridge and the
semiconductor creates unwanted contact resistance which affects maximum output Q of the couple. Even the best
thermoelectric material is useless without feasible fabrication process providing low contact resistance. Couples are
usually connected in series forming so called „battery powered (electro-thermal) cooler”. To achieve higher thermal
gradient while maintaining the cooling performance, single thermo-components are connected in cascade –
individual batteries need to be well insulated. Ceramic with good thermal conductivity is usually used for this
purpose.
P-type -Zn4Sb3
P-type TAGS
P-type Bi2Te3
ZT
P-type PbTe
Temperature [°C]
Fig. 2.7 ZT values for various semiconductor thermoelectric converters in relation to temperature
Zn4Sb3 has three known structural modifications: phase is stable under –10 °C, phase in –10 to 492 °C range
and -phase is stable from 492 °C to its melting point 566 °C. Zn 4Sb3 is therefore present as -phase in practice with
forbidden band width of 1.2 eV. -Zn 4Sb3 modification is strongly doped P-type semiconductor. Interesting fact
-1 -1
about -Zn4Sb3 is its low thermal conductivity (lower limit of only 6 mW·cm ·K at 250 °C) which
Si
Micro- alloyed Si - Ge with varying Si:Ge ratio is another perspective material. Combination of Si alloyed with
5 at. % Ge doped with 0,3 at. % B or 0,4 at. % P can decrease the thermal conductivity by 5.7 or 6.7 % compared to
pure Si (at 298 K). Seebec coefficient S of doped Si has local maximum at charge carrier concentration of (3
19 -3
4)·10 cm , while in doped Si0.97Ge0.03, such maximum has not been observed. Thermoelectric
efficiency ZT of N- and P-type Si0.95Ge0.05 increases linearly with temperature T and values of ZT = 0.90 and 0.57
at 1073 K have been measured.
La0,9(Sr1-xCax)1,1CoO4
Conducting characteristics and promising magnetic properties predetermine polycrystalline ceramic materials of
La0,9(Sr1-xCax)1,1CoO4 type for thermoelectric application.
Thermoelectric properties of CoSb3 can be further enhanced by Ni, Pd and Pt doping (donor additives). Hall
mobility, Seebeck coefficient and electric conductivity are strongly affected not only by donor concentration but
also by impurities. High thermoelectric efficiency value ZT = around 0.85 (at 800 K) was achieved by doping by
both Pd and Pt.
Eutecic
point
T
o
[ C]
Lead-free solders
Many aspects need to be considered while proposing new solder. The solder joints must be highly conductive in
both heat exchangers and in electrical engineering applications. Good fluidity and ability to fill the cavities in the
joint, so it is not gas-penetrable is necessary for heat exchangers, radiators and water pipelines. Electric
conductivity is important for application in electric engineering, thermal conductivity for heat exchanger
manufacture. Another aspect, especially for electronic application, is low melting point – this prevents damage of
the circuit board or components during soldering. Alloy components must be available in sufficient amounts, also
must be environment-friendly, non-toxic and of course reasonably costly.
For reasons mentioned above, the Sn-Pb solders are being slowly replaced by other tin- based alloys. Numerous
lead-free tin binary alloys have been proposed. Alloys with eutectic or close to eutectic composition have been
chosen for their narrow solidification interval. Alloys 99Sn1Cu, 97Sn3Cu, 96.5Sn3.5Ag, 95Sn5Sb, 91Sn9Zn and
42Sn58Bi are time-proven. Important attributes of these alloys are wetting properties, melting point, mechanical
properties and also resistivity.
Wetting is defined as an ability of liquid solder (flux) to establish contact with clean surface at given
temperature. Fluidity is the ability of liquid solder (flux) to spread across the surface of the base material at given
temperature. The only condition required from all solder alloys is good wetting of the substrate. Wetting is closely
related to the surface tension between the interfaces. Inter-atomic forces form bonds across the interface which
quickly spread across the whole contact area. Formation of intermetallic compound is necessary condition for good
wetting properties and firm connection between the solder and the metal. Intermetallic compounds can still form
after the weld joint has solidified (under melting point) – for example by atomic diffusion.
Ultrasounds soldering
The soldered place, along with melted solder is subjected to mechanical oscillation of 5 to 100 kHz which
disintegrates the surface oxide layer and allows the metals to be connected. Ultrasound soldering is facilitated by
either submerging into bath or local soldering. The solder is firmly connected to the magnetostriction oscillator
(nickel sheet) which generates heat. Current, produced in special generator, flowing through the wiring oscillates
the sheet; the solder is heated by eddy currents.
Brass solders
Most common hard solders are from copper and its alloys. Brass solders (copper also belongs to this group) are
used for steel soldering in protective atmosphere. Increasing the zinc content decreases the melting point, but solder
becomes brittle. Therefore, brasses with more than 65 % Zn are not recommended. Slow heated brass solder
develops pores – zinc is evaporated and the chemical composition changes. Phosphorus copper solder Cu- P8 is
recommended for soldering of brasses with more zinc; its melting point is low even without flux (710 °C).
Nonetheless, this solder is unsuitable for steel soldering, because the joints are brittle. Brass solders with added
silver increases their fluidity and adhesion, while keeping the porosity low. Therefore, the Ms-60 Ag is frequently
used. Alloy with added nickel has high strength and toughness. Brass solders are suitable for welding of small
components with similar shape made of for example: steel, cast iron, copper and its alloys, and for soldering of
plates from sintered carbides.
Silver solders
Silver solders have favorable properties – generally lower melting point, higher strength and toughness and
corrosion resistance. The amount of silver in the alloy also changes its color which is utilized in jewellery.
Common solders contain up to 65 % of Ag. Alloys with more silver exhibit lower melting points, increased
toughness and electric conductivity.
Silver solder characteristic: relatively low melting point, forms tougher and stronger joints, more chemically
stable than brass solders. Silver solders with phosphor addition are suitable for copper alloys that require low
soldering temperature. Solder with suitable combination of Ni, Mn and Ag forms very strong joints suitable even
for soldering of corrosion-resistant steel. Cd addition lowers the soldering temperature, the joints are stronger while
keeping their toughness.
Silver solders are viable for soldering of copper and its alloys, nickel and nickel alloys, steel, corrosion resistant
steel, cast iron and grey cast iron, sintered carbides, metal ceramics, tungsten, tantalum, molybdenum and titanium.
Gold solders
Gold has, either as solder or as an alloy with other elements, unique properties. Its main asset is the fact that its
surface does not oxidize. Soldered joint is corrosion resistant and can withstand high temperature changes; it also
has very high ductility. Gold is used as diffusion solder. In form of foil or wire, copper/copper plated components
be diffusive soldered at temperature around 450 to 550 °C, that is in temperature range, where only a few other
solders can be used. Soldered joint is stable up to 800 °C. Gold micro-wires with aluminum sputtered substrate can
be also diffusive soldered this way. This procedure is employed for most of the semiconductor chips with terminal
contact joints.
Eutectic alloy AuSn20 has soldering temperature 280 °C. It is used in form of cuts for vacuum sealed covar
component joining (with gold deposited in advance), e.g. for hermetical sealing of ceramic casings. This alloy
exhibits best vacuum tightness of the joint of all known soft solders while having high thermal-shock resistance.
Gold alloyed with antimony or silicon in form of foil is used for reactive soldering of silicon chips coated with
silver or gold in semiconductor and integrated circuit production. Combination of temperature and ultrasound is
used to start the reaction in aerial conditions. Hard gold solders wet many soldered metals and alloys.
Palladium solders
Palladium substantially enhances soldering properties of Ag-Cu and Ni-Mn hard solders. Soldered joints have
high mechanical strength at elevated temperature, are more ductile and also have higher corrosion resistance.
The biggest asset of palladium is the inhibition effect on diffusion of Ag- Cu solders into FeNi and FeNiCo
alloys. Mentioned properties along with relatively low cost of palladium and silver predetermine the palladium
solders for complex, reliable and heavily thermal-loaded joints.
These solders are used for soldering FeNi and FeNiCo with copper and its alloys, titanium, zirconium,
beryllium, tungsten, molybdenum and corrosion resistant steel. It is also viable for soldering of metal-coated
ceramics. Soldering usually takes place in furnace with protective atmosphere without flux.
Pb+Sn
Ag wire (diameter) d [mm] 0.06 0.18 0.47 1.0 1.4
Breaking current I [A] 2 6 25 60 102
Ag Ag
Pb+Sn
Ag Fig. 2.10 Principle of lowering the melting point of Ag conductors in fuses
Material solution:
Covar (54 % Fe + 29 % Ni + 17 % Co) - l = (4.4 to 5.2) ·10-6 K-1 in temperature range T = 20 ÷ 300 °C. Material for
vacuum tubes, especially suitable for connection with covar glass.
W, Mo, Ta
Ir, Rh , Pt - expensive
Intensity of magnetic field is proportional to the number of coil threads and passing current – very high number
of coil threads in superconductive coil lowers the current necessary to generate magnetic field with similar intensity
as in common magnet. Superconductive coil can therefore generate very strong magnetic field (several tesla units)
with only tens of amperes – normal coil would require small power plant to achieve such intensity. Fig. 3.1 shows
the difference in size of standard and super-conductive coil which would be required to generate magnetic field of
similar intensity using 100 A current. Small superconductive magnet generates field with double the intensity.
However, this chapter starts with advantages of zero specific el. resistance, employed for energy distribution.
This attribute is undoubtedly useful, however, the high cooling expenses of the superconductive wire limit its wider
spread. The research of high-temperature superconductive materials is very promising. Classical low -temperature
superconductors are pure metals and their alloys (superconductivity manifests at temperatures under 23 K – liquid
helium with boiling point of 4.23 K is therefore needed), the high-temperature superconductors have, in average,
critical temperatures of 90 K, some even 136 K, that is, over the boiling point of nitrogen (78 K). Liquid nitrogen is
relatively affordable coolant. Common low-temperature metal-base superconductors have good formability and
conductor fabrication is simple. High- temperature superconductors are generally very brittle ceramic materials and
their fabrication is very demanding. Two separate ways, how to overcome brittleness of these materials, are
nowadays studied – rolling of polycrystalline material in silver matrix (capillary) and welding or chemical
deposition of crystalline superconductive layers on flexible, strip-shape, substrate. Modern technology allows
production of superconductive strips up to roughly 1.5 km length.
Fig. 3.2 Non-superconductive material Fig. 3.3 Superconductive material placed in magnetic
placed in magnetic field. fields keeps the bulk in its former state (zero
The field penetrates the magnetic field intensity), and the outer magnetic
material freely. field is therefore pushed away.
What does this has to do with levitation? Let’s look at another pair of figures. Superconductive material at
temperature higher than critical temperature (therefore non-superconductive) placed in magnetic field generates
shielding currents which are quickly dissipated by el. resistance and the field enters the material. If we cool the
superconductive material bellow its critical temperature it becomes superconductive. Passing the critical
temperature does not alter the magnetic field in the “superconductor”, no current is generated and the magnetic
field present in the material before cooling get “frozen” inside the material in the same state as before cooling .
In fact, magnetic field does not flow directly through superconductive material but through microscopic non-
superconductive channels. These channels are called vortexes or superconductor holes. Shielding currents flow
through their perimeter, therefore shielding the surrounding superconductive material from magnetic field inside
the vortex. Each vortex carries on or more elementary units, so called quanta of magnetic flow.
Any change of the exterior magnetic field (increase or decrease of intensity or even change in polarity or
distribution) generates shielding current on the surface of the superconductor, compensating the change.
Consequently, if the permanent magnet is moved in any direction, the generated currents oppose the change,
pushing the magnet back to its original location. It is thus held in a magnetic gap – it is hard to escape from this
gap. This situation is a complete opposite to the situation with two permanent magnets. Not only can the magnet
float above the superconductor, it can also hang under. This state is stable as long as is the superconductor cooled.
Relative position of magnet and superconductor is stable to some degree – the magnet can even keep significant
weight afloat together with it. Such device placed in vacuum (negligible air friction) with perfectly rotary
symmetrical magnet (not just by dimensions but also the shape of the magnetic field), can operate as lossless
Fig. 3.4 Cross-section of the MagLev train and the U-track. Fig. 3.5 MagLev on a test track in
Superconductive coils interacting with the track coils are Yamanashi at about 200 km/h
depicted
Possible applications of superconductive materials are numerous – from super-fast switches (base component of
future computers), high-power transformers, circuit breakers in power plants or gigantic ships with magneto-hydro-
dynamic propulsion. Hundreds of other possible applications are being experimented with in laboratories, waiting
for their chance.
Metal
Low-temperature
superconductors
Tc 10 K Tc 90 K
Fig. 3.6 Critical temperatures for low- and high-temperature superconductive materials
Superconductor placed in magnetic field with (intensity lower than critical) produces currents on its surface
generating magnetic fields with opposite polarity and intensity (also bellow the critical level). Magnetic induction
of superconductor is therefore zero – superconductor is an ideal diamagnetic material. This is utilized for
shielding against external magnetic fields.
It has been experimentally shown, that superconductivity can be canceled even by relatively small magnetic
induction (10-3 to 10-1 T). This, so called critical limit of magnetic induction Bc and it is temperature dependent.
Outcomes of the superconductivity: Total magnetic flowing through zero-resistance circuit is zero (unless the
el. resistance changes).
Current flowing through the superconductor, generating magnetic field on its surface which exceeds the critical
limit of magnetic induction Bc causes the material to lose its superconductive properties. Critical current Ic is
affected not only by the type of the material but also by its shape. Superconductors with copper cover are used in
applications, where current spikes can be expected - these can cause the transition from superconductive to normal
state – copper can provide another current path for
some time. This is especially important for high-
temperature superconductors which are usually non-
conductive in normal state. I [A] σ [A.m-2]
Occurrence of superconductivity σc
I
depends on : temperature T,
external magnetic field H, c
transport current I. σ
Exceeding these so called critical limits
superconductivity disappears (Fig. 3.7). H
Superconductive normal transient by magnetic field is Tc T [K]
reversible.
Fig. 3.7 Relationship between superconductivity
Hc
occurrence, temperature T, magnetic field intensity H [A.m-1]
H and transport current I
Superconductive range
Magnetic field penetrates only the thin surface layer of the superconductor – depth of penetration L.
Superconductive – normal borderline continuous transient - coherent length D.
Superconductor characterization:
a) By the parameter two basic types are recognized: Superconductors of
the type I ... < 0.7 (e.g. for Pb: = 0.4). Superconductors of the
type II ... (e.g. for Nb3Sn:
Current flowing through type II superconductor placed in magnetic field allows the fluxoids to move due to
existence of Lorentz forces. However this generates heat and the critical values decrease. This can, in some cases,
cause the transient to normal state. To prevent the migration of fluxoids in the superconductor material
(homogeneous), lattice imperfections (foreign atoms, dislocations and others) are induced – these hinder the
movement of fluxoids by binding them. Such superconductor is called non-homogeneous type II superconductor
or hard superconductor. Magnetization curve of such material is no longer reversible and hysteresis loop is
formed causing energy losses in alternating field.
The type II superconductors are utilized almost exclusively. So far, over a thousand superconductive compounds
and alloys have been discovered. Superconductive materials can be also prepared from materials which are non-
superconductive in their pure state. Nb-Ti, Nb-Zr and Nb-Ti-Zr alloys and Nb 3Sn, V3Ga, Nb3Ge, Nb3Al and
Nb3Al0.8Ge0.2 compounds are the most-frequently utilized superconductive materials.
Behavior of type I superconductors in magnetic field is depicted on Fig. 3.8 a), type II on Fig. 3.8 b).
B R B R
B B
R R
0 Hk H 0 Hk1 Hk2
a) Type I superconductor b) Type II superconductor
Fig. 3.8 Dependence of magnetic induction B in superconductor and its electrical resistance R on
intensity of external magnetic field H at T < Tc
Low-temperature superconductor fabrication technology
Nb-Ti-Zr alloys and intermetallic compound Nb3Sn have, so far, the widest variety of application.
Nb-Ti-Zr – solid solution => expected good formability => allows for wire fabrication.
Fabrication technology of superconductive materials is based on its character and properties. Nb-Zr, Nb-Ti and
Nb-Ti-Zr alloys are typically manufactured by melting in vacuum electric arc furnaces. After casting, they are
worked, typically by rolling, to produce desired semi-finished products – wires and rods. From these, various
conductor types are produced by rolling the semi-finished product together with copper coating or by drawing. The
conductors are produced as single-lined (diameter of Nb line is typically 0.2 mm, diameter of copper coating about
a) Superconductive wire, b) Cu matrix. Cross section of superconductor with 102 Nb-Ti threads
Fig. 3.9 Design of chosen superconductors
Other technologies of multithread conductor production are based on diffusion of tin from brass to niobium or
through the copper cover.
It is necessary to mention that zero resistance providing loss-less current transport is of a great benefit, however,
this is offset by the necessity of cooling by expensive liquid helium.
a. Critical temperature Tc
Real achievable temperature 3/4 ÷ 2/3 Tc.
At 3/4 Tc, the critical intensity of magnetic field Hc reaches about a half of low-temperature limit Hc0 and critical
current density Ic is about ~ 1/4 of the limit value.
Example: with liquid nitrogen N2 (78 K) as and coolant, superconductive material with Tc ~ 100 K can be used.
Material of YBa2Cu3Ox type (also called YBCO or „1-2-3“) with Tc = 95 K represents borderline option.
(Material operated at 293 K would need to have the Tc about 400 K).
b. Upper limit of magnetic field intensity
YBa2Cu 3Ox (1-2- 3) has extremely high value of limit field intensity. It depends on the relative orientation of the
field and a, b, c axis of the orthorhombic lattice of the superconductor. Values are in range of 30 T (c axis) to
about 200 T (a, b axis) at T = 4.2 K.
c. Critical current density σc
Requirements: σ > 103 A·mm-2 for „volume“ conductors (power plant industry applications) and for thin
superconductive foils.
2 -2
YBa2Cu3Ox: σ ~ 10 A·mm at 4.2 K and magnetic field intensity of 6 T.
The σc decreases rapidly: at to 77 K and 6 T to 1 ÷ 10 A·mm -2. Reaching highest possible σc over T = 78 K => basic
requirement for practical application of volume high-temperature ceramic superconductors. Prerequisites for
application: σc ~ 103 A·mm-2, T = 78 K, magnetic field intensity 5 T.
Epitaxy-grown thin foils: σc ~104 A·mm-2, T = 78 K at very low magnetic field intensity (meet the microelectronics
requirements).
d. Chemical stability
1-2-3 type material is reactive at normal temperature. Humidity and CO 2 cause deterioration => formation of
hydroxides and carbonates. Prevention: protective coating! The coating prevents the diffusion in outer layers
(especially in thin foils) – otherwise degradation of superconductive properties.
e. Radiation effect
High-temperature superconductive ceramic is more sensitive to radiation than conventional superconductors
(potential problems with application in extremely strong magnets in fusion reactors).
f. Frequency effect
Conventional superconductive materials show some resistance in AC configuration; energy losses in oxide-based
superconductors are expected to be smaller.
g. Material characteristics
High strength => danger of brittle fracture, suitable preparation methods => deformation before final oxidation =>
coil wiring.
High-temperature conductive materials known up to this date are basically ceramic. First was the LaBa2Cu 3O7-x
compound. Shortly after that, more favorable physical properties have been discovered in the similar material with
lanthanum replaced by yttrium (YBa2Cu3O7-x). Best superconductive properties are reached with x close to 0.1. In this
material, also called “1-2-3“, yttrium can be replaced by almost any rare earth elements or by scandium. Materials with
yttrium replaced by cerium, praseodymium or terbium do not exhibit superconductive properties.
Structure of the ceramic superconductors of 1-2-3 group is orthorhombic similar to the structure of perovskite –
difference is the oxygen deficiency. Structure with fully-occupied oxygen spots would have the YBa 2Cu3 O9
formula and the compounds would have layered structure of BaCuO 3:CuO:BaCuO3 type. Superconductive phase of
YBa2Cu 3O7- x formula is formed by heating the compound above 500 °C – this forces the oxygen to escape the
structure, and the structure (yttrium and barium ions separated by layers of copper and oxygen) develops oxygen
vacancies.
0.382 nm
Y
Ba Ba
oxygenkyslík
vacancyk e
měď
- Deformation caused by lattice transformation => micro-cracks initiation => micro-crack prevention
(fine-grained structure after sintering, grain size under 1 micrometer).
„Filled profiles“
Superconductive powder is placed in Ag tube.
Tube is then formed by drawing or rolling.
Tube protects the superconductive material from the environment; in the case of semiconductor malfunction can
operate as el. conductor.
Thermal treatment close to melting point, σc ~ 1.5·104 A·cm-2, magnetic field up to 26 T.
Permeability susceptibility :
r < 1 ( < 0) r > 1 ( > 0) r >> 1 ( >> 0) r >> 1 ( >> 0) r 1
Materials:
Cu, Au, Ag Al, Sn, Pt Fe, Co, Ni Ferity MnO
Matters can be, based on the magnitude of relative permeability r and susceptibility divided in four groups:
1. r 10 diamagnetic materials
2. r = 1 = 0 magnetically neutral materials
3. r > 1 > 0 paramagnetic and antiferromagnetic materials
4. r >> 1 >> 0 ferromagnetic and ferrimagnetic materials
4.2.1 Diamagnetisms ( 0 r 1)
Not temperature or magnetic field intensity dependent = const. Superconductor
extremely high susceptibility in superconductive state = – 1
4.2.3 Ferromagnetism 0 r 1
Ferromagnetic matters are characterized by:
5
- r ~ 10 .
- Incomplete outer electron orbitals 3d in Fe, Co, Ni, lanthanides have similar properties.
- Atoms of ferromagnetic materials can, under certain circumstances, become paramagnetic.
- Elementary magnets interact with each other ~ thermal oscillation parallel configuration.
- Strong magnetization in so called Weiss domains (saturated magnetization) even without external magnetic
field.
- These domains are separated by so called Bloch walls, where the magnetic moment direction is altered.
- Crystalline lattice – regular distribution of atoms in crystal.
- Collectiveness of regular atom distribution in crystal lattice.
- Increasing the temperature above material specific, so called Curie temperature Tc, causes ferromagnetic
material to become paramagnetic.
Metal Fe Co Ni Gd
Tc [K] 1043 1404 631 290
Existence of ferromagnetic domains with magnetic moments arranged parallel (due to the atomic interactions)
under the Currie temperature is characteristic for ferromagnetic matters. Atoms need to be close enough to interact
this way.
Heating of ferromagnetic matters causes inter-atomic distances to increase, number of atoms with parallel
orientation of magnetic moments decreases; at Curie temperature, the domains vanish as well as the
ferromagnetic properties. Despite existence of domains with magnetic moment, the ferromagnetic matters appear
to have zero magnetic moment. Domains organize themselves to minimize the energy of the system. This
configuration is depicted on Fig. 4.1; magnetic moments of four neighboring domains act as a separate magnetic
circuit.
Domain is a macroscopic structure, with length and width of several nanometers and about 0.001 to 0.1 mm
thickness. Intensity of magnetic field inside the domains is very high – the domains are saturated. Neighboring
domains are separated by layers called Bloch walls. Their thickness is usually around 10 -6 to 10-4 cm, i.e. ~ 500 to
5000 of inter-atomic distance units in crystal elemental cell. Domain structure can explain many important
phenomena and properties of ferromagnetic materials, e.g. their magnetization in external magnetic field.
Ferromagnetic domains are dimensional structures grouping to form larger structures.
Magnetization curve and hysteresis curve
Closely corresponds to the domain structure of ferromagnetic matters.
J = f (H), J magnetic polarization [T], H magnetic field intensity [A·m-1]
Br
Decreasing the intensity of external magnetic field of previously magnetized ferromagnetic matter results in
lower values of magnetic induction compared to the first magnetization (Fig. 4.3). This phenomenon is called
magnetic hysteresis. If the magnetic field is canceled, the induction does not drop to zero but remains at certain
value of Br, called remanent magnetization (or remanence). Magnetization gradually drops to zero if we
magnetize the ferromagnetic in opposite direction. Magnetic field intensity which nulls the remanence is called
coercivity, Hc. Increasing the opposite magnetic field intensity increases the magnetic induction up to saturated
state. If decreased, the induction changes according to curve no. 3. Reversing the polarity of magnetic field again
increases the intensity to value corresponding to saturated state. The magnetization cycle is hereby finished, its
graphic representation is maximum hysteresis curve. Hysteresis also manifests during cyclic magnetization, if the
intensity of altering magnetic field exceeds at least one region of irreversible shift of domain walls.
Ferromagnetic matters are, for example, metals (α – Fe, Co, Ni, Gd, Tb, Dy, Ho, Er, Tm), their alloys, and also
some compounds of ferromagnetic metals with rare-earth elements (particularly RCo 5 compounds, where R can be
Sm, Ce, Y, Pr etc.). Alloys comprising of non-ferromagnetic elements, such as Mn-Cu-Al alloys (Heusler alloys),
also Mn-Ag-Al and others also can be ferromagnetic.
4.2.4 Antiferromagnetism
Antiferromagnetic matters (antiferromagnetics) are solids with crystalline structure, magnetic domains are
formed due to the interaction of their atoms. Magnetic moments of atoms in these are in antiparallel
configuration. The opposite magnetic moments cancel each other; that is why antiferromagnetics have zero total
magnetic moment up to the critical temperature (Néel temperature or Curie temperature), where the antiparallel
configuration disappears. Above critical temperature, these materials behave the same as paramagnetics. Examples
of antiferromagnetics are Mn and Cr, some oxides (e.g. MnO, FeO, NiO) and other compounds (MnSe, FeCl 2,
FeF2, CuCl2 etc.). Amorphous antiferromagnetics are also known.
4.2.5 Ferrimagnetism
Is a special case of antiferromagnetism and occurs in crystalline matters. Ferrites are typical example.
Ferrites – iron oxide Fe2O3 + oxides of other metals with oxidation state +2.
Sub-grid has different crystallography, with different type of ions which contain nodes.
The grids are not equivalent.
Spontaneous magnetization of sub-grid A is different than sub-grid B.
Magnetizations are not canceled by each other.
Ferrites exhibit some magnetic moment.
BS
Shape of the hysteresis loop is mostly affected by chemical composition and state of lattice which corresponds
to the fabrication process, such as cold or hot rolling, annealing or quenching.
10
magnetization is described in relation to the crystal axis. Iron α grain
Fe
with BCC lattice is easier to magnetize along its (100) axis, slightly
0 Co harder in the (110) direction. The least favorable direction for
magnetization is (111). However in nickel (also BCC lattice), the
- (111) is the easiest magnetization direction.
Magnetostriction
10
exhibits as changes in length and volume of ferromagnetic
-2
material by magnetic field. Its magnitude is described by
magnetostriction coefficient λ which increases with magnetic field
0 intensity and has its limit at saturation state – Fig. 4.5.
H [kA .m·m-1]-1]
Silicon steel
Silicon decreases hysteresis losses, Fe + 0.5 – 4.5 Si
Application: rotary machines and transformer sheets for high voltage transformer stations.
Silicon steel is broadly used magnetic material in electrical engineering. Magnetic properties of strips produced
from silicon electro-technical steel can be enhanced by grain crystallographic orientation, so called texture. This is
achieved by combination of forming and rolling. Rolling direction is aligned with the easy magnetization vector.
Electro-technical silicon steels are classified by the rolling technique and texture:
* hot-rolled, isotropic, silicon content (3.5 % to 4.6 %). Employed mainly in media transformers with
guaranteed permeability at low magnetic field intensity and for core of low-frequency chokes.
* cold-rolled, isotropic, silicon content around 2.5 %. Mainly for rotary machines.
* cold-rolled, anisotropic, silicon content about 3 %. Produced in form of thin strips with directional structure.
Often have insulation coating. Application: electromagnetic immobile and rotary machines, appliances.
Application of sheets with directional structure in transformers leads to reduction in size and weight, resp.
increase in throughput compared to the sheets without directional structure. Transformer with the same throughput
weighs about 25 % less, about 15 % less material for wiring is used. Special types of sheets with oriented structure
for production of small transformers, chokes, measurement, control and impulse transformers are rolled to
0.05 mm thickness and width up to 100 mm, later cut into 10 to 30 mm strips. Used for production of ring (toroid)
transformer cores or divided cores (by slicing the core).
Insulation for the sheet surface is very important. The surface of the hot-rolled sheets is oxidized – this is
sufficient form of insulation for transformers operated up to 50 Hz. Larger transformers with operation frequency
above 120 Hz require the sheets to be insulated from one side with sodium silicate or varnish. Cold-rolled strips
must be insulated, since their surface is smooth and metal-glossy. For small motors and transformers operated up to
50 Hz, the oxide layer is produced during annealing in continuous furnaces at 550 to 800 °C.
Fe-Co alloys
These alloys exhibit the highest magnetic induction. Fe – Co 35 % has Bmax = 2.4 T, Fe – 50 % Co – 2 % V has
-6
Bmax = 2.35 T and can be hot-rolled to thin sheet. This alloy has high magnetostriction at Bmax ( max = 80·10 ).
4.4.2 MAGNETIC METALLIC GLASS
Amorphous magnetic materials are also referred to as magnetic metallic glasses. They belong to the group of
soft magnet materials. Metallic glass are not crystalline as common metallic materials, however they preserve the
metallic appearance and have characteristic physical, mechanical and chemical properties which surpass the
properties of crystalline materials of similar composition. These materials are homogeneous, movement of Bloch
walls is effortless – this is why they are much magnetically softer compared to the similar crystalline material.
Some properties of metallic glass (e.g. specific density, compressibility) are identical to crystalline material.
Metallic glass is not anisotropic, it has high radiation damage resistance. No noticeable structural changes have
been detected in metallic glass even after strong irradiation.
Mechanical properties: very high yield strength, surpassing all metals, however some steels have similarly
high fracture toughness. High yield strength is, from the physical point of view, caused by very low mobility of
dislocations. This is due to the disorganization of the base structure and absence of slip planes. Metallic glass is
prone to plastic deformation when strained due to its instability; however it can withstand severe plastic
deformation when bent, sheared or pressed.
Corrosion properties: surface of the metallic glass develops homogeneous protective oxide layer, resistant to
corrosion, especially in chlorides. Cr supports the formation of protective film.
Magnetic properties of metallic glass: Fe based metallic glass can be magnetized easily, especially compared
to the Permalloy. Easy magnetization of metallic glass is related to the high mobility of magnetic domain walls in
the matrix. The eddy currents are, thanks to its high el. resistance, hindered. High mobility also corresponds to
excellent macroscopic magnetic properties. This, consequently, explains low specific watt losses (W/kg). Metallic
glass is utilized in, for example, production of transformers, amplifiers, switches, recording heads etc.
Table 4.4 Comparison of values for two transformer types (15 kVA)
Parameter Silicon steel Metallic glass
Current 2.5 A 0.12 A
Watt losses 112 W 14 W
Losses in copper 210 W 166 W
Total loss 322 W 180 W
Energy savings 0 1250 kWh/year
Temperature o o
100 C 70 C
Table 4.5 Critical cooling rates vc of some materials to produce amorphous structure
Metallic glass is perspective soft magnetic material. Stream of liquid metal is jetted on fast rotating,
intensively cooled drum – the metal is thus prevented from forming crystalline structure. Produced strip has about
10 to 50 m thickness and width in the magnitude of tens to hundreds of mm. It can be bend, formed, rolled and cut.
Disadvantage of metal glass is its thermal instability. Heating above certain temperature starts the crystallization
process; the favorable properties disappear. This temperature depends on the alloy composition and usually does
not exceed 300 °C.
The „glass-state” can also be reached in alloys that can be super-cooled in liquid state.
Alloy types: Fe, Co, Ni +10 30 (B, C, P, Si, ...). General formula of magnetic glass (Fe,Co,Ni)80 (B,C,P,Si)20.
Table 4.6 Properties of some metallic glasses
.
Composition BS [T] Hc [A m-1] max
.
Fe80B20 1.8 6.4 1 105
.
Fe40Ni40P14 B6 0.5 0.8 4 105
1.2 3.0 . 5
Co74Fe6B20 3 10
Chemical composition , Hc, shape magnetostriction. These materials exhibit several-magnitudes higher resistivity.
Fe86B7C7 – magnetic polarization in saturated state JS = 1.77 T; 3 times higher than Fe-Si alloy.
. -1
Co58Ni10Fe5B10Si11 Hc = 0.4 to 0.5 A m .
Metal glass has, compared to the electrotechnic steel, about five times lower losses from eddy currents.
Hysteresis loop
The shape of J(H), resp. B(H) curve in Fig. 4.7 is characteristic for hard magnetic material. The shape of curve
from + Hmax to –Hmax and back defines the hysteresis loop. It corresponds to the distribution of magnetic domains
(Weiss domains) in the material. Two phenomena are distinguished: transport of domain walls and rotation of
magnetization vectors. The first phenomenon takes place in lower-intensity fields, the other in the saturated state
region. Fig. 4.7 depicts the differences of the two hysteresis loop types – the difference is provided by the additive
component µo H. B(H) relationship is more common in technical use.
Fig. 4.7 J(H) and B(H) relationship for Fig. 4.8 Demagnetization curve of a magnet
hard magnetic material
Demagnetization
Demagnetization is decrease of total magnetic polarization of magnet. This can be achieved by external source
of magnetic field of opposite polarity. This process is called demagnetization.
Working point
Instead of the whole hysteresis loop, just the second quadrant (demagnetization curve - Fig. 4.8) is displayed;
this part depicts the operation region of the permanent magnet and characteristic points. Working point Pw of
permanent magnet is characterized by Bw, Hw values. After demagnetization, this point shifts from remanence to
the left along the magnetization curve to final Pw. In optimal case, Pw is identical to (BH)max.
Means of magnetization
Permanent magnet needs to be magnetized after its fabrication. Magnetic field intensity should be at least triple
the coercivity of magnetized material. Materials with low Hc value can be magnetized after assembling the circuit.
Special electromagnets are typically used for magnetization of permanent magnets; their coils are powered by very
strong pulse current. Other methods: discharge of condenser battery or application of special pulse power sources.
Multi-pole magnetization
Basic type is the double-pole magnetization, i.e. magnet with one north and one south pole. This configuration
allows the quick magnetization of block or cylindrical magnets (axial magnetization). Some magnets require use
of multi-pole magnetization. For example, strips from magnetic rubber can thus generate higher holding force; in
case of ring-like magnets for electric motors, the number of poles affects the smoothness and rotational speed.
Multi-pole magnetization is facilitated by special configuration of field segments.
Magnetic anisotropy
Suitable material must be chosen, if, for example, higher value of (BH)max product is required. In many cases,
higher characteristics can be attained in similar, magnetically anisotropic material. This can be achieved during
fabricating by strong field or magnetic tension with specific orientation. This way, directional structure is formed
and subsequently the magnetically anisotropic properties manifest. The magnetic properties in the direction of the
main magnetization axis are substantially stronger than in isotropic permanent magnet, the properties in
perpendicular plane are hindered. To fully utilize the anisotropic magnet, it must be magnetized in the direction of
the main axis.
Curie temperature
When utilizing permanent magnets, close attention must be paid to operating temperature, so it does not exceed
0.4 of Tc [K] which is considered to be the „safe zone”.
Irreversible changes
Thermal changes and deterioration of magnetization are caused by reversible and irreversible processes.
Irreversible changes are closely related to the microstructure and magnetization mechanism of the material. The
structure relaxes over time (also influenced by temperature) and the internal energy of the system decreases.
Macroscopic consequence is deterioration of magnetization, eventually of other parameters.
Surface treatment of magnets
No surface treatment.
Varnish. Some types of magnets, especially metallic, are attacked by corrosion. If operated in normal
conditions, synthetic varnish, powder warmish or nitro-varnish are sufficient to prevent this.
Galvanic metal coating . Magnets such as Fe-Nd-B and Alnico sometimes need to be coated with metal to
provide sufficient corrosion resistance in aggressive environments, i.e. wet or warm atmosphere or in water. This
coating must have good abrasion resistance, adherence to the surface and stable dimensions. Nickel coating is the
most common type of galvanic metal coating.
6. Vicalloy– (Fe32–Co52–V14) is processed by quenching, tempering and cold-forming. These alloys acquire their
magnetic properties after forming. They were designed for demanding applications (watches, magnetic recorders,
-1
special motors, memory chips etc.). They have high remanence of 0.6 to 1.45 T at Hc = 36 kA·m . Their price is
very high due to high Co content.
8. Other alloys
Alloys without ferromagnetic properties represent another group of materials. Magnetic properties are attained
by forming, preceded by quenching and followed by aging. Examples of such alloy are Silmanal (Ag89–Mn9–
Al5) with remanence 0.05 T at Hc = 46 kA·.m-1, Oertit 900CP (Pt78 -Cr22) remanence 0.65 T and Hc = 385
-1
kA·m . High cost limits their use to special applications (wristwatches, space devices).
Ferrites are oxide materials (ceramics) derived from ferric oxide Fe2O3 . Their magnetism is facilitated by non-
compensated antiparallel configuration of magnetic moments in domains (ferrimagnetics). Their crystal lattice is
similar to inorganic materials of spinel, garnet or hexagonal structure (HCP). Crystal lattice of ferrite is very
complex.
3. Magnetic composites
Magnetic composites consist of fine- grained ferromagnetic or ferrimagnetic material and suspension medium.
Suspension medium is usually natural or synthetic resin, or thermally hardened granulate. Oldest composite was so
called high-frequency iron. There are two groups of these composites. The organic material in the first group works
only as a bonding agent, organic material in the second one also substantially affects the properties of the
composite (so called magnetic rubber).
Hard magnetic ferrites pressed with plastic belong to the first group. Bakelite ferrite is produced from
formaldehyde resin. Their advantages are precise dimensions of the product and good machinability. Polyethylen-
ferrite, shortly pefer, is an agglomerate of branched polyethylene and fine-ground ferrite powder. Content of ferrite
powder is chosen so it could be shaped by injection by common spraying machines. Injection products are precise
and do not need to be machined, they are only magnetized. This process is suitable for low-cost production of large
batches of same magnets.
Magnetic rubbers belong to the second group. They are produced by mixing of flexible bonding agent
(thermoplastic resin or rubber) and powder with permanent magnet properties. This causes certain deterioration of
magnetic energy per unit of volume, however complex shapes or thin magnets can be produced this way. Magnets
are characteristic for their elastic properties and are fabricated in form of flat plates or strips with 2 to 5 mm
thickness. Arbitrary shapes can be cut from plates. Shaped pressings can also be produced. The composite is
Materials utilized in the form of thin layers are deposited on non-magnetic substrate of less than micrometer
thickness. These have polycrystalline character and domain size is smaller than grains. Grain boundaries hinder the
movement of domain walls and thus increase coercivity. Unlike the powder materials, the concentration of
ferromagnetic material in the thin layer is much higher which corresponds to higher saturation induction. Big
drawback is its price and complicated fabrication technology – vacuum vapor deposition or sputtering. The layers
are fabricated from the basic ferromagnetic materials (Fe, Ni, Co) their alloys with rare earths and ferromagnetic
oxides.
b. Materials for magneto-optic recording
Magneto- optic recording is one of the most purpose- full method how to store data on solid replaceable discs.
This method utilizes the properties of the given material around Curie point. At this temperature, the material has
very low coercivity (good ability to store the magnetic information). Coercivity decreases to less than 1/10
compared to the coercivity at 20 °C. Changing the magnetization is therefore easy and does not require strong
magnetic fields.
Focused beam of infrared laser diode is used for recording (wavelength of emitted beam 830 nm) . Recoding on
disc is a thermo-magnetic process. Magneto- optic layer on the surface of the disc is locally heated by pulse (for
about 500 ns) laser with about 10 ÷ 20 mW power. After this, the information is recorded by magnetic field H.
During the cooling of the layer, the coercive filed Hc disappears and effective magnetization field Hef (stronger than
Hc) records the information. Hef consists of inner demagnetization field and the functional field. The direction of
remanent magnetization corresponds to the field Hef.
Amorphous rare earth alloys (20 % Gd or Tb) with ferromagnetic metals Fe and Co are commonly used. These
are prepared by cathodic sputtering. Other perspective materials are garnets (Tc = 160 C) and Co-Pt, Co-Ca alloys,
operating at frequency above frequency of visible with Tc = 250 400 C.
Up to this date, amorphous alloys, such as Gd-Tb-Fe or Tb-Fe- Co are utilized in commercial magneto-optic
discs as memory medium. High-density and multi-layer recording materials are candidates for the near future.
Multilayered Co/Pt disks have more controllable perpendicular magnetization and also 100 % remanence. Co/Pt
films offer higher corrosion resistance and wider rotation angle with beam of narrower wavelength (300 400 nm)
which enables higher recording density when using blue light laser recording diode.
Co-Ni/Pt materials were developed for magneto-optic media, since their Curie temperature and Tc are lower
than those of Co/Pt material. Lower Tc is required for more reliable low-power recording along with high number
of R/W (read/write) cycle.
Computers are equipped with optical drives , utilizing laser light or electromagnetic waves close to the visible
light for part of the data reading and recording. It’s a periphery used for data storage on optical discs. Most of the
drives can also record data. The recorders are also called burners or writers. Optical disc drives are utilized for data
archiving or exchange. Along with flash memories, they replaced the floppy discs and tape recorders. The essential
parts of optical recording drive are: semiconductor laser, laser focusing lens and photodiode which receives the
light reflecting from the disc surface. Laser light wavelength for CD is 780 nm, for DVD 650 nm and for Blu-ray in
HD DVD 405 nm. Basic principle of burning is same for all systems. Single-recordable disc has a polycarbonate
substrate with deposited gold layer. Laser beam burns through the polycarbonate and stops at the gold layer, thus
creating a pit.
As an example of the gradual process of silicon refining with final purity 5N (99.999 % Si) you can see the
schema:
Metallurgical Si HCl SiHCl 3
rectification SiHCl 3
reduction pure silicon
1 % impurities 300 °C raw pure H2 1100 °C 10 ppm
impurities
coefficients
a) Admixture B reduces melting point TmA (ko < 1),
b) Admixture B increases melting point TmA (ko > 1).
ko 1 ko exp DL
-1
where v – the macroscopic speed of movement of the phase boundary (cm·s ),
– the thickness of the sub-laminar diffusion layer (cm),
2 -1
DL – is the diffusion coefficient of the admixture B in the melt (cm ·s ).
The theory proposed by Burton, Prim and Slichter assumes that the solidification front is characterised by the
formation of a thin diffusion layer whose thickness changes in relation to the intensity of mixing the melt. The
thickness of this layer also depends on natural convection and viscosity of the melt, and the speed of rotation of the
crystal (forced convection) and on the nature of the flow in the melt (turbulent or laminar) and only to a certain
degree on the crystallization rate.
Equation (5.3) indicates that at the growth rate v = 0 the value kef = ko which means that as the solidification rate
decreases, the degree of enrichment by the impurity in the melt for the case in which ko < 1 increases. At the rate v
= , kef = 1, and there is no distribution of the admixture in the macro-space of the ingot. The effective distribution
coefficient can be determined by experiments and is described by the following equation:
kef = CS(o) / CL( ),. (5.4)
where CL( ) is the concentration of the admixture B in the main volume of the melt.
In order to ensure that the process of refining of the main substance to remove the admixture is efficient, it is
necessary to select the minimum possible speed of movement of the solidification interface and to reduce the
thickness of the diffusion layer it is necessary to increase the intensity of forced convection of the melt (by
Crystal Melt
0 lo
Fig. 5.3 Principle of directional crystallization
10
k = 0.1
λ=5% Co =1
1
C(x)
0.1
Cn (x)
1
C(x)
b = 0.1 L o
Co =1 k = 0.8 Co =1 n=3
1
k = 0.5 n=4
k = 0.2 n=5
k = 0.1 n=6
0.1
k = 0.01 0.1 n=7
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 n=8
Final
distribution n=9
n = 10
0.01 0.01
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9
x/lo x/lo
Fig. 5.7 Concentration profiles of zone melting Fig. 5.8 Concentration profiles for zone melting
after a single passage of the zone for different after 1–10 passages of the zone including final
values of the distribution coefficients k. distribution
The comparison of the concentration profiles of zone melting and directional solidification for k < 1 indicates
(see Fig. 5.5 and Fig. 5.7) that the degree of depletion in the admixture in the narrow zone in zone refining is, as a
result of the smaller volume of the zone, lower in comparison with the mother liquid can spread widely along the
entire length during directional solidification. Consequently, after the single passage of the zone, the level of the
concentration of the foreign admixtures in the ingot subjected to a single zone of the melting is higher in
comparison with directional solidification.
Figure 5.8 shows the increase of the refining effect after 1–10 passages of the zone. Comparison with directional
solidification and its concentration profile indicates that zone melting is an efficient method of refining only if the
process is carried out as a multiple refining process. Depending on the parameters of b, k and lo, it is possible to
obtain the final or limiting distribution.
A shortcoming of zone melting and also directional solidification when used as the refining method is the joint
presence of the impurities with k > 1 and k < 1 in the main substances. Therefore, prior to selecting these refining
methods, it is necessary to evaluate the presence of all impurities in the main substance and their possible
distribution in relation to the values of the distribution coefficients or select a different method of removal of these
impurities.
A greater effect may be obtained by the so-called zone refining with the removal of material in which the
final small part of the zone refined substances is gradually removed, for example, after every pass of the zone, from
the end of the ingot (at k < 1). This process is characterised by the highest degree of enrichment with admixtures,
yield of refined material. Zone melting is used, in addition to the production of high purity substances, also for the
preparation of micro-alloyed parts of the zone refined ingot or for growing single crystals of high purity substances
(silicon, germanium, refractory metals, etc.).
5.3.3 Drawing the crystal from the melt - Czochralski method of single crystal
preparation
The method is based on a procedure in which a seed crystal is immersed in the melt in the crucible, the seed is
partially melted and, subsequently, is withdrawn from the melt at a lower rate, Figs. 5.9 c) and 5.11. The
temperature distribution in the cross-section of the crystal must be symmetric in relation to the axis of the crystal;
this is supported either by the rotation of the seed or rotation of the crucible with the melt, or rotation of both. The
rotation of the crystal and the melt ensures sufficiently high homogeneity of the melt and the minimum width of the
diffusion layer at the solidification front. The crucible with the melt is placed inside the closed space of the furnace
in vacuum or an inert atmosphere to prevent oxidation of the melt. The heating source is represented by resistance
or induction heating. The usual drawing rate is 1·10 -4 – 1·10 -3 cm·s-1 at a rotation speed of 0.1 to 1 s-1. The
temperature of the melt in the crucible should be maintained at required value slightly above the melting point of
the given metal with a relatively high accuracy of ± 1 K.
The temperature distribution along the axis of the crucible in the Czochralski solidification equipment is
shown schematically in Fig. 5.11 b). The isotherm, corresponding to the solidification temperature of the substance,
is situated above the surface of the melt. The temperature in the crucible increases in the direction to the bottom of
the crucible. The single crystal seed and the growing crystal are used for the efficient removal of heat from the
solidification front. The form of the surface of the melt is affected by gravitation and the surface tension of the
melt. The rate of withdrawal of the crystal, the speed of rotation and the temperature of the melt in the crucible also
affect the shape of the crystal–melt phase boundary. At a high
temperature of the melt or a high withdrawal speed, the
solidification isotherm is situated above the surface of the melt
resulting in a decrease of the diameter of the crystal. On the other
hand, a decrease of the temperature of the melt and the speed of
withdrawal increases the diameter of the crystal which is utilised
in practice.
Plasma heating is used in the production of special alloys and, in particular, in the metallurgy of high- purity
alloys. Plasma forms as a result of thermal ionisation of the gases – argon, nitrogen, hydrogen and other inert gases
in the electric arc. Generators of low- temperature plasma include plasma torches working with the electric arc
concentrated by a nozzle with the joint aerodynamic effect of the flowing gases. The VŠB-TU of Ostrava (Czech
Republic) developed a plasma torch with the continuous stabilisation of the electric arc running between a water-
cooled cathode produced from thoriated tungsten and a copper nozzle used as an anode. Other types of plasma
torch (plasmatrons) are based on the ionisation of gas in the high frequency field operating with frequencies of up
to several tens of MHz.
water
1) solidification mould, 2) plasma torch, 3) external jacket,
gas 4) carrier pipe, 5) internal jacket, 6) front end of the
water
solidification mould, 7) furnace flange, 8) guide screw, 9)
shift carrier, 10) electric drive, 11) cooler.
water
The Department of Non-ferrous Metals, Refining and Recycling of the VSB-TU of Ostrava developed, for
special applications in the preparation of high purity metals by zone melting, a plasma furnace with a horizontal,
copper, water-cooled solidification mould operating with a low-temperature plasma torch (Fig. 5.14). The furnace
can be used for melting metals with medium melting points (Fe, Co, Ni) and with high melting points (Ti to Mo),
and for special high-alloyed alloys (Fe–N, Ni–Ti, Al–Fe–Mo, etc.) which cannot be often prepared by other
methods because of the high volatility of components (Cr). This furnace operates with a slight excess pressure of
the atmosphere of the ionised gas or a mixture of gases (Ar, Ar–N 2, Ar–H2) and produces temperatures of up to
10000 K in the plasma arc.
Plasma heating is used on an increasing scale for the intensification of metallurgical processes, for the refining
of metals and preparation of single crystals of refractory metals, alloys and compounds. The plasma-forming gas
+ –
also ensures additional refining of metals by the reactions Ar + e with the melt, the reaction of oxygen and
hydrogen in plasma with admixture elements in the melt, and the removal of volatile substances from the
superheated melt.
coil for HF
heating
movement
ofhezone
molten zone
spindle
direction
vacuum
system
Fig. 5.17 Equipment for electron beam zone melting in vacuum by the
DC high
floating zone method.
voltage
source a) section through melting equipment,
12000 V
In electron beam zone melting, in addition to the effect of zone refining, a significant role is played by
secondary processes. They cause the generation of gases and evaporation of admixtures with a high vapour tension
-3 -6
in the conditions of working vacuum of 10 – 10 Pa. The single crystals of metals, produced by this method, are
not perfect, especially when the bar diameter is large. During the growth of the crystal and its solidification,
samples contain a steep temperature gradient, the crystal–melt interface is curved and, consequently, mechanical
stresses form in the crystal. Nevertheless, this method has been used for the growth of single crystals of W, Mo, Ta
and Nb with large, slightly disoriented subgrains and with the dislocation density of less than 10 4 cm-2 inside the
subgrains.
Fig. 5.18 Verneuil method for pro the preparation of single crystals of oxides
Preparation of single crystals from the gas phase, the vapour–liquid–solid (VLS)
method
A droplet of a solvent is placed on a crystal substrate and at the given temperature the droplet is additionally
saturated by means of a chemical transport reaction, resulting in the formation of a supersaturated solution. The
resultant concentration gradient leads to diffusion in the droplet and to crystallization on the substrate. The result is
the growth of a sharp-tip ‘whisker single crystal’, with the tip of the crystal covered by the solvent.
The first stage of growth of this crystal is the formation of nuclei. In the preparation of crystals from the gas
phase, the condition for the growth of nuclei is the essential super-saturation of the vapours. According to the
current views regarding crystal growth mechanisms, the bonding of atoms to the crystal takes place on steps
formed by a screw dislocation. In this case, the formation of a closely spaced plane is never completed and results
in spiral growth of the crystal, i.e. a whisker crystal. Theoretically, a single screw dislocation is sufficient for the
growth of a crystal at low super-saturation. Crystallization from the gas phase was used to obtain whisker crystals
of Ge, Si, Fe, Sn, Zn, Ag, Cu, Ni, etc, with the mechanical strength close to the theoretical value.
The single crystals of refractory metals with a low vapour tension are efficiently produced from the gas phase of
their volatile compounds. This is carried out by chemical transport reactions of compounds in the gas phase on the
surface of the crystal substrate. This method has also been used to produce, for example, single crystals of W, Mo,
Nb, Ta and other refractory metals. The initial materials are halides of these metals, for example, chlorides or
fluorides. In this method, the chloride or fluoride of the appropriate refractory metal is placed in the evacuated
space and heated to transfer it to the gas phase. Using a hydrogen flow, the vapours of tungsten hexachloride WCl 6
are supplied to the heated tungsten fibre (approximately 1000 °C) where WCl 6 is reduced. The reduced tungsten
settles on the heated fibre. When selecting suitable cooling rates, temperature and concentration conditions, a single
crystal grows on the seed. As a result of the combined reduction of the mixtures of chlorides, it was possible to
obtain alloys of the type W–Mo, Mo–Nb, W–Nb and superconducting layers of Nb 3Sn on a metallic substrate.
Rapid solidification
During cooling from a melt, metals and alloys solidify at the melting (liquid) temperature. However, as soon as
10 -1
the cooling rate exceeds 10 K·s , the mobility of the atoms is theoretically restricted in such a manner that they
solidify by the amorphous mechanism, i.e. retain the atomic structure of the melt. At present, it is possible to obtain
6 8 -1
cooling rates of 10 – 10 K·s and, consequently, the amorphous state can be produced only in certain metallic
systems, for example:
metal – metalloid: Fe80P13C7, Au81Si19,
metal – metal: Cu60Zr40, Ni60Nb40.
In rapid solidification, a melt jet is sprayed between two rapidly rotating cooled copper rolls. In this case, the
amorphous (microcrystalline) solid metallic ribbon with a thickness of several millimetres and several centimetres
wide solidifies between the rolls during several microseconds. In fact, the ribbon is injected into the space behind
the rolls. In this case, coiling is the technical problem.
Amorphous metals, the so-called metallic glasses, formed during rapid solidification, are homogeneous
materials without grain boundaries and are characterised by high strength and elasticity. In contrast to commercial
glasses, they can be compressed by up to 50 %. They are characterised by high corrosion resistance, electrical
connectivity and can be easily magnetised and, taking into account low electric losses, they already replace
conventional transformer sheets. In heating to temperatures higher than recrystallization temperature, amorphous
materials may change to the crystalline state and, consequently, it is important to consider the stability of metallic
glasses. The results of these rapid solidification technologies (in addition to metallic glasses) are also structural
variants of microcrystalline materials with the grain size smaller than 1 μm.
The processes of rapid solidification are used at present for processing not only magnetically soft materials but
also for modification of, for example, the properties of aluminium alloys based on super-duralumin Al–4.5Cu with
1 – 3 % Li. In the case of aluminium it is also possible to obtain a higher solubility of iron, nickel and manganese
(3 – 8 %), the solubility of chromium, zirconium and cobalt in copper is increased, and in steels it is possible to
increase the solubility of carbon, boron, silicon and phosphorus. Similarly, for special applications it is possible to
produce improved types of dispersion-hardened materials with a higher concentration of ultrafine precipitates. The
processes of rapid solidification also indicate the trends for materials with the application of trace elements and rare
earth metals (lanthanides) in promising areas of electrical engineering and microelectronic materials.
2 PH3 2 P + 3 H2
2 AsH3 2 As + 3 H2
B2H6 2 B + 3 H2
vaporvstup (gas)plynůinlet/par
rozdvaporělova(gas)č distributorplynů/par
quartzkřemennýcoverzvon
copperměděnácoilcívka
octagonal pyramid
graphitefitovýcarriernosičofSiSidesekwafers
Si deskawafer
4 kHz
powerzdroj
source
odpadwaste odpadwaste
rotace
rotation
degasificationASANACE
Fig. 5.20 Equipment for deposition of Si epitaxial layers (coils of the inductor are placed closely beside
themselves)
Silicon epitaxy is technically the best-more exacting chemical process at the technology of the production of
micro-chips
Various types of epitaxial reactors exist. One of the most common types of the modern reactors is the barrel
reaction vessel (Fig. 5.20), but also the horizontal reactors with rotating one- or more-plate discs. Reactor is formed
with a carrier of Si wafers made from very clean graphite (99.9995 %), coated with the 100 µm thick protective
layer from silicon carbide SiC (99.9999 %). Graphitic carrier of Si wafers in the form of multi-contest pyramid is
placed in a quartz cover. Around the cover is wound a copper coil, which ensures heating of the graphite and then
also Si wafers throw inductive currents at frequency of 4000 Hz. Reactive substances flow to the cover from above,
i.e. H2 (flush of the reactor), then H2 + HCl (clean-up of the surface of silicon wafers by etching with highly pure
gaseous hydrogen chloride), H2 + SiCl 4 + PH3 (epitaxial growth), H2 and in the end inert N2 (flush of the reactor
Horizontal reactors with rotating one- or more-plate discs use either radiation heating (bar screens of halogen
bulbs are placed above or below quartz reactor) or induction heating – see Fig. 5.21. Their advantage is high
homogeneity and high reproducibility of parameters of deposited layers reached especially by construction of
injectors of the gaseous mixture, rotation of Si wafers and by using of intensely cooled quartz pipes with small high
(small distance between wafers and top wall of the reactor cuts non-homogeneity of the fluxion rising at space
above Si wafers owing to natural convection). Disadvantage of these reactors is lower manufacturing capacity.
LPE methods:
A) Non-stationary methods – during the epitaxial growth is changed the temperature – crystallization is non-
isothermal.
1) Nelson's turn-over method – see Fig. 5.22. The substrate is placed on the top part of the container, at the
bottom finds the saturated solution in melt, on whose surface swims a saturated solid phase. As you can see from Fig.
5.22 a) and from the time path of the temperature - Fig. 5.22 b) the melt is after the turn-over in contact with the
substrate and starts the process of the crystallization behind gradual temperature decreasing.
a) b) turn-over
2) Rotary variants LPE. Instead of turn-over process of the bowl is used the rotation of tube.
3) Dipping variants LPE
This method is used for the production of magnetic monocrystalline layers on the different kinds of garnets and
for preparation of other semiconducting layers. The saturated solution of the melts is found in the crucible (e.g .
Ga-Gd-garnet) in PbO·B2O3. First is the solution in melt under-cooled, i.e. is super-saturated and after them the
substrate is deep into melt and all system is cooled down.
4) LPE cassette method – see Fig. 5.23. In stage a) a cassette with a solution in the melt (e.g. Ga) is found in the
separate space containing material, from which will be crystallize new epitaxial
layer. The solution is slightly overheated, i.e. it is in non-saturated state. The
substrate is placed outside this space in separate parts of the cassette (slide-valve).
Both parts of the cassette are each other movable. After the temperature equalization
on To will the slide-valve move the substrate below the melt – stage b). At that a
slight melting-down of the substrate takes place thereby to removing the failed
surface layer. In stage c) happens the growth of epitaxial layer during reducing
temperature on T1. Having finished crystallization, i.e. after achievement of needed
thickness of layer, the slide-valve moves the substrate into the original position. The
whole system is cooled on temperature T2.
Application of LPE:
III V II VI
With using the LPE method are prepared the layers especially for semiconductor compounds of A B or A B
types on the ground of high volatileness (flightiness) of one or both components at melting temperature of the
compound that lies considerably high above the melting temperature or sublimation temperature of basic
components. Compound GaP has melting temperature higher than 1500 °C, while gallium only 29.8 °C and
phosphorus 44 °C, whereas phosphorus has high tension of vapors at increased temperatures. Method LPE is
substitutable also for the production of so-called „bubbly memories", i.e. memories with cylindrical domains and at
most of other optoelectronic devices.
SUBSTRATE CARRIER
Fig. 5.24 Scheme of the MBE process
GaAs substrate
at the growth of epitaxial layers on the
GaAs substrate
Typical working
temperatures in effusion
cells: Ga 1000, As 300, Si
1100, Al 1200, Be 900,
substrate 550 [oC]
screening oven
Examples of applications:
Radiation incurred on PN junction in laser diodes spreads to all directions. Carrier injection incurred with the
current passage in permeable direction and their recombination is very effective method for conversion of
electricity on luminous energy. To development of the luminescent diodes and namely laser diodes it is of cardinal
importance the discovery of super-injection in the double hetero-structure. The active recombination region is in
this case surrounded by layers (GaAl)As P- and N-type with bigger width of the forbidden band and with the
smaller refractive index – see Fig. 5.26. Such ordering has very favourable influence on own recombination
processes and on optical, resp. light guide characteristics of the whole luminescent system.
heating of carrier and engine
cryogenic panels cooled with variable rotation speed
with liquid nitrogen electron gun for
RHEED
gauge for monitoring
of beam flow
screens
window
fluorescent
screen rotating holder of
the substrate
quadrupole mass
spectrometer
2 Dt
where supplement of the error function erfc(z) = 1 – erf(z) = 1 – 2z (5.11)
exp dy
y
2
0
b) Diffusion from the limited source, i.e. from infinitely thin layers into unconfined body
2
Cp exp x
4D t
C( x,t ) , (5.12)
2 Dt
where Cp is the the total quantity of diffused material, i.e. total number of atoms outspread on the unit surface [in
cm-2], or surface concentration of the diffused substance.
Coating of admixtures on the substrate surface can be realized by using of several technologies:
- thin layers deposition of impurity or compounds containing an admixture,
- coating of admixture in the form of saline solution on the substrate surface,
- leaching of admixture or its compounds on the surface by the sorption from solution,
- ionic implantation,
- short - term diffusion under the conditions of the constant surface concentration.
Diffusion coefficient D is dependent on the temperature according to the Arrhenius formula – see (5.13). The value
of activation energy Q is bigger (or it is necessary to give more energy for the atoms jump), the diffusion is slower.
Diffusion mechanisms
In crystalline materials are regular atoms in nodal points of the crystal lattice, where occupy the power
advantageous position. Point defects are found here too. Owing to oscillations of the lattice (thermal motion of
atoms) can come to a jump of atoms from the one equilibrium position to the other, which constitutes diffusion
process. According to way of jumps we can distinguish the next diffusion mechanisms – see Fig. 5.27:
a) substitution mechanism (double or cyclic exchange of atoms in nodal point of the lattice) – Fig. 5.27 a),
b) interstitial mechanism (migration of atoms from the one among-nodal position to the second – Fig. 5.27 b),
c) vacant mechanism (migration of an atom on the vacancy place) – Fig. 5.27 c),
d) interstitial substitution (or dissociative) mechanism (atoms walk up from substitution positions to the
interstitial, migrate on the interstitial positions and in the place of vacancy they walk again to the substitute
position) – Fig. 5.27 d), e.g. diffusion Cu in silicon,
e) migration of atoms along the linear and plane defects.
a) b) c) d)
Fig. 5.27 Basic conception of diffusion mechanisms
NA
ND
x = xj x
xj2 xj1 x
Fig. 5.28 Concentration of donors and acceptors after gradual diffusion of phosphorus and boron in Si. On the left:
NP junction (example of the semiconductor diode), on the right: NPN junction (transistor)
As the source of the admixture in Si and Ge can be used vapors or liquid films of the elements 3. or 5. groups
periodic table, eventually their allied substances. Thin films as diffused source are created using the chemical
reaction of vapors with semiconductor surface. The liquid film can be formed also with alloy, which will originate,
if the vapor pressure of an admixture at diffusion temperature is bigger than is the solubility in solid semiconductor.
Diffusion of admixture atoms proceeds at temperatures 100 200 °C below the melting point of semiconductor.
Except the source with endless capacity is used also the source with constant amount of admixture. It is realized
using deposition of the element on the semiconductor surface. It is difficult, therefore it is usually created from the
planar source with pre-diffusion, namely in short time at lower temperature or alternative method is the deposition
of the element using chemical reaction to create the glass layer on the semiconductor surface. As an example may
have been a diffusion of phosphorus from P 2O5 vapors. P2O5 acts on a substrate as far as creates the phosphorus-
silicate glass. Phosphorus from here diffuses into semiconductors and creates N-type semiconductor layer. The
glass layer is then etched.
Diffusion equipments
1. Diffusion in the vacuum system with one temperature zone proceeds in the closed evacuated quartz tube, in
which is found semiconductor and admixture. The tube is placed in the oven warmed at required temperature.
Vapor pressure is given by amount of the admixture and its temperature.
2. Diffusion in the system with one temperature zone under atmospheric pressure is carried out on air or in
flow of the suitable gas (e.g. in nitrogen) – see Fig. 5.30. Admixture is deposited on the semiconductor surface
in the form of boron-silicate or phosphorus-silicate glass.
3. Diffusion in vacuum with two temperature zones - see Fig. 5.29. In the first zone (on the left) with the source
of admixture is maintained temperature corresponding to the vapor pressure of admixture. In the second zone
proceeds the diffusion. In vacuum is evaporation rate of silicon comparable with the diffusion rate.
4. Diffusion in the system with two temperature zones under atmospheric pressure. Vapors are transferred
with carrier gas (e.g. nitrogen). Distribution of admixtures depends on the temperature. Diffusion of admixtures
into semiconductors proceeds several hours at high temperatures.
Sources of admixtures:
- pure elements (P, As, Sb, Ga …),
- oxides (P2O5, As2O3),
- halides (BCl3, BI3 , BBr3),
- silicate layers on the semiconductor surface (B2O3·SiO2). They have low melting point and create the
continuous layer on the semiconductor surface.
Sii wafersdesky
5 cm
+ vacuumVakuováchakomberora
Ar
AlCuSi
+
Ar
CATHODE ANODE
KATODA ANODA
rotary drum
otočný buben
(target) (frame)
(target) (rámeček)
Fig. 5.31 Principle of the sputtering method (metallizing of Si wafers with Al-Cu-Si alloy)
One of the important quantities determining the sputtering rate of individual components in Al-Cu-Si alloys is
so-called sputter yield. It is relationship of the number of atoms sputtered component released from target through
one Ar+ ion. Sputter yield is dependent on a kind of sputter material, and on energy of inert gas.
1 – anode,
2 – cathode,
3 – gas inlet,
4 – plasma,
5 – extracting electrode,
6 – ionic beam,
H – magnetic field
Ge
Si
Se
InSb
TiO 2
Cu 2O Glass Mica
Fig. 6.1 Resistivity ranges of materials for
Metals,
alloys Semiconductors Organic insulators
electrical engineering
10 - 6 10 -4 10 - 2 10 0 10 2 10 10 6 10 8 10 10 10 12 1014 10 16 10 18 10 20
4
1,E-06 1,E- 4 ,E- 2 1,E+ 0 ,E+02 1,E+04 1,E+06 1,E+08 1,E+101,E+12 1,E+14 ,E+16 1,E+18 1,E+20
·cm]
a) diamond lattice b) cubic (sfalerite ZnS type) c) hexagonal (wurtzite FeO type)
Fig. 6.2 Schema of atom spatial configuration in Si and in A-B semiconductive compounds
Table 6.1
Both silicon and germanium crystallize in diamond lattice (Fig. 6.2a) and are characterized by typical covalent
bond. Covalent bond comprises of electron pairs with opposite spin moments on the same energy level. Four
atoms (neighboring) are symmetrically arranged around each atom in semiconductive material; they are all
connected to the central atom by bond facilitated by single valence electrons. Central atom is in the middle of
tetrahedron, its corners represent the four closest atoms. Two neighboring atoms of crystal share two electrons,
exchanging them; it cannot be differentiated which electron belongs to which atom. Any atom of the lattice is
therefore surrounded by eight electrons; half of each of those electrons belongs to this atom. Electron octet is
important mostly for maintaining the electro-neutrality of the atom, since atom therefore achieves the electron
configuration of inert gasses He, Ne, Ar, …
2 2 2 2
Bond hybridization principle: Isolated Si atom has the valence shell configuration of (ns) (np) - s p for short,
where n is the main quantum number – Fig. 6.3 a). To achieve the electron octet the atom must share another four
electrons from four closest atoms with the same valence shell configuration. This however violates Pauli principle,
since there can be only two electrons in s orbital (with opposite spin). Each Si atom must therefore place one
electron to the higher-energy orbital p, and each of those atom
a therefore has the (ns)1(np)3 shell configuration, sp3 for short - Fig. 6.3 b). Hybrid
tetrahedron bonds sp3 are typical for all elementary and compound semiconductors; all
atoms with covalent bond hybridize this way. The angle between the axes defined by the
atom couples is 109°28’. The contraindication of the hybridization is high inner energy
b between atoms which, from physico-chemical point of view, exhibits itself by high
melting point, high hardness and high molar enthalpy of melting compared to the
metallic materials – comparison with common metals is in Table 6.1.
Melting points, molar melting enthalpy and entropy of chosen metals and semiconductors
Tm Hm Sm Tm Hm Sm
Metal Semiconductor
[°C] [J·mol-1] [J·mol-1·K-1] [°C] [J·gat-1] [J·gat-1·K-1]
Cu 1083 13437 9.91 Si 1420 46470 27.45
Ag 961 11300 9.16 Ge 940 34720 28.62
Al 660 10800 11.58 GaAs 1238 52600 34.83
Fe 1538 15200 8.4 GaP 1511 62700 35.16
Ni 1453 17920 10.38 GaSb 706 32400 33.08
Ge H, N, C, Si, Sn, Pb, Ne, Ar dtto dtto Cu, Ag, Au, Zn, Cd, Mn, Ni, -
Fe, S, Se, Te
GaP H, N, B, Al, In, As, Sb S, Se, Te, Si, Ge, Be, Mg, Zn, Cd, C, (Cu) Cr, Fe, V, O, Ni, Mn, Ag, Au Si, Sn (up 1018 cm-3 donor)
Sn
GaAs H, N, B, Al, In, P, Sb S, Se, Te, Si, Ge, Zn, Cd, Be, (Li) dtto Si, Ge (up 1018 cm-3 donor)
Sn
InP H, N, B, Al, Ga, As, Sb S, Se, Te, Ge, Sn Zn, Cd, Be, Mg, (Cu) dtto -
InAs H, N, B, Al, Ga, P, Sb S, Se, Te, Si, Ge, Zn, Cd, Mg dtto -
Sn
InSb H, N, B, Al, Ga, P, As S, Se, Te, Sn, Zn, Cd, Mg, Si, Ge, (Cu) dtto -
(Li)
The relationship between concentration of major carriers and resistivity in semiconductors is approximately:
1/ N 1 (6.3)
maj e
maj
Si is utilized exclusively in single crystal form for semiconductive component fabrication, e.g. transistors,
diodes, thyristors, integrated circuits, microprocessors, memory modules etc.
Si has wider range of operation temperature and higher reliability and lifetime compared to the Ge
components.
Other Si compounds: SiC, Si3N4, SiO2 – insulation and dielectric layers.
Silicon is the second most abundant element in the Earth crust. Silicon cannot occur in the crust in its pure form.
Lithosphere comprises of about 25 wt. % of silicon in form of various compounds. The most common silicon
compound is silicon oxide and various silicates.
The precursor for metallurgical silicon is quartz – SiO2; silicon is produced by reduction of quartz by carbon
(coke) in electrical furnaces:
SiO2 + 2 C = Si + 2 CO
Metallurgical silicon is not suitable for application in semiconductor industry as it contains about 0.2 wt. % of
impurities (predominantly aluminum and iron). All methods of high purity silicon production are based on
acquiring a suitable compound from metallurgical silicon, its refinement and then decomposition of this compound
yielding pure silicon. Silicon halides and halogen silanes are suitable precursors for this process. Nowadays, the
trichlorsilane – SiHCl3 is being used almost exclusively; silicon chloride – SiCl4 or silane - SiH4 are also used,
but rarely. The first two compounds are produced by reaction between hydrochloride (pure, anhydrous) with milled
metallurgical silicon at 280 ÷ 380 °C. Ongoing reactions are summarized by these reactions:
Si + 3 HCl = SiHCl3 + H2, Si + 4 HCl = SiCl4 + 2H2.
Reaction conditions can be altered to shift the reaction equilibrium to favor one or the other product (either SiHCl 3
or SiCl4). Additives present in the metallurgical silicon react simultaneously to form chlorides (FeCl 3, AlCl3, BCl3,
PCl3 and so forth). Formed compounds are then refined (SiCl 4 and SiHCl3 are liquid at normal temperatures).
Refining, i.e. repeated distillation produces high-purity trichlorsilane. Refined trichlorsilane usually contains about
5 ppm of carbon, mostly in form of methyltrichlorsilane CH 3 SiCl3, phosphorus and boron is kept bellow 1 ppm.
Reverse decomposition of pure trichlorsilane is facilitated by reduction in hydrogen at 1000 to 1100 °C,
summarized by (simplified) reaction:
SiHCl3 + H2 = Si + 3 HCl.
2200 °C
TRICHLORSILANE
3. step distillation 99.999 liquid
SiHCl3 32 °C
1100 °C
Fig. 6.4 Sequence of technological operations during refining of silicon and production of single crystals
Most of the elements exhibit so called retrograde solubility in silicon, i.e. their maximum solubility
temperature is bellow melting point of silicon and the solubility decreases (sometimes even by an order of
magnitude) during cooling which has significant importance for crystallization refining of silicon.
III/V N P As Sb
B BN BP BAs BSb
Al AlN AlP AlAs AlSb
Ga GaN GaP GaAs GaSb
In InN InP InAs InSb
A•
GaAs
e)
c)
.
1,5 1018
. 19 -3
5.1019 5 10 cm
Production of semiconductive AIIIBV, AIIBVI compounds with high vapor pressure (GaAs, InAs, CdTe,
CdxHg1-xTe)
- Higher pressure melting. Gas pressure must correspond to the dissociation pressure of the liquid.
- The temperature of the recipient must be higher than the condensation temperature of volatile compound.
- Melting in quartz ampoules.
- Excess of the volatile (As, P, Cd, Zn…) component outside the reaction chamber – compensation of their
evaporation from the melt liquid of AIIIBV or AIIBVI which have high melting point well above melting point of
the basic elements.
Preparation of singe crystals under boron oxide liquid is a significant improvement. It is referred to as LEC
(Liquid Encapsulated Czochralski).
GaAs, PbTe, PbSe single crystal preparation - shielded with melt B 2O3.
B2O3 properties: hygroscopic (necessary to anneal at 600 °C and normal pressure and then at 1000 °C in vacuum),
the enamel is transparent. For higher temperatures, CaO, BaO, CaCl 2, BaCl2, KCl and others are used.
GaAs, InP, InxGa1-xAs Hf. transistors and MIC High electron mobility
GaAs, InP Hf. generators and amplifiers, Gunn diodes Gunn phenomenon
GaAs Hf. generators and amplifiers Cascade effect
GaAs Frequency multipliers, parametric amplifiers, Voltage dependency of PN
tuning transition capacity
GaAs Electro-acoustic amplifiers, signal delay circuits Piezoelectric effect
GaAs,GaAsxP1-x, Recombination of carriers on
AlxGa1-xAs, GaP, Luminescence diodes
PN transients emits ray
(In,Ga)·(As,P)
GaAs,GaAsxP1-x, Generation of pair on PN
InxGa1-xAs, AlxGa1-xAs, Radiation detectors
transient emits ray
(In,Ga)·(As,P), InSb
GaAs, AlxGa1-xAs, Coherent light sources (laser diodes) Recombination of carriers by
(In,Ga)·(As,P) injection
Note: Hf. – high frequency, MIC – monolithic integrated circuits
d) AlSb – Properties: grey powder with metallic gloss, pure AlSb is stable in air.
Application: solar cells, diodes.
GALIUM COMPOUNDS
a) GaN – Properties: low solubility in acids and alkalis, oxidation in air at 1000 °C.
Application: epitaxial layers of GaN – luminescence blue-light diodes, complex luminescence devices,
colored imagining components.
d) GaSb – Properties: sfalerite structure, cleavage plane (110), alloyed with Se, Te: N-type.
Application: laser diodes ( = 1.6 m), low-noise hf. diodes.
INDIUM COMPOUNDS
a) InP - Properties: dark grey crystals, metallic gloss, cleavage plane (110).
Application: laser diodes.
c) InSb - Properties: exceptional electron mobility, low vapor pressure of the components.
Application: Hall generators, laser diodes (5.2 m) - InSbxAs1-x, laser diodes emitting light of specific
wavelength.
Compounds with heterogeneous structure (quaternary semiconductive compounds) on, e.g. InAs/GaSb/AlSb
basis, have significant importance for optoelectronic devices, because they have similar lattice. The band gap and
conduction band width can be adjusted by changing the element ratios.
Ferroelectrics: TiO2+ (oxides La, Nb, Ta, Ba, …) e.g. SrO·TiO2, PbO·TiO2, BaO·SnO2,
CaO·SnO2, CrO·SnO2, MgO·ZrO2
Application: ferroelectric and piezoelectric materials – see chap. 7, PTC thermistors (positive temperature
coefficient).
Garnets: Ln3Fe5O12, where Ln is suitable lanthanide, e.g. Gd, Sm, Eu, Tb (with the exception of Nd, Pr, La
and Ce) or yttrium – e.g. garnets of GGG type Gd3Ga5O12, YIG type garnets Y3Fe5O12 or YAG
garnets Y3Al5O12.
Quartz: SiO2
15 16
Properties: Dielectric compound, wide band gap W = 8 eV and = 10
·cm at 300 K. 10
Application: Dielectric and insulation layer for fabrication of integrated circuits, quartz tubes, crucibles
for Si melting, diffusion processes, epitaxy, light guides.
Sapphire: Al2O3
15 16
Properties: Dielectric compound, wide band gap W = 5 eV, = 10 10 ·cm at 300 K, melting point of Tm
= 2050 °C, modification: - Al2O3 – hexagonal, -Al2O3 – cubic.
Application: Dielectric substrates for silicon epitaxial layers preparation, various applications in
optoelectronics.
I I
EH F v EH v F
B B
Fig. 6.7 Principle of Hall effect and determination of conductivity type in semiconductive materials
Force F bends the charged particles trajectories in such manner, that opposite charges are generated on the
opposite sides of the plate and transverse voltage EH is generated. Direction of EH depends on the type of
predominating charge carrier, i.e. semiconductor type (Fig. 6.7). Deviation of the charge carriers continues until the
generated electric field EH compensates the effect of the magnetic field. Then, the force F which is applied to the
charge by the electric field, is equal to the Lorenz force and the system reaches equilibrium, because the total force
on the charge moving through the plate is zero.
This so called Hall voltage UH = EH d measured between the top and the bottom side of the plate can be
described by equation:
UH R H I B ; RH 1 , (6.5)
d N qe
Alternating current, even high-frequency current, passing through Hall sensor can be altered by changing the
magnetic field; altered voltage can be collected as alternating Hall voltage. This configuration is called Hall
moduler.
Hall sensors can be utilized for mathematical operations (multiplication) and for low-frequency current
generation or as components of electronic switches controlled by magnetic field.
Small ventilators
Distance measurement
Other applications: various proximity, safety, water level and pressure switches and others.
Passivacetion
Emitorittor
BázeBasis
PolníOxideoxid
Metallizationce KColektlector
Fig. 6.11 Arrangement of
EpitaxníEpitaxial vrstvalayer electro-active components of
one transistor on integrated
circuit.
Horizontal dimensions of the
transistor are (145 x 80 µm),
vertical dimensions are (5 to 20
InsulIzolacetion
µm). Thickness of the Si wafer
SubstrateSubstrát UtopenáDiffusionvrstvalayer (pad) – cca 340 m.
PropojeníBurriedlayerutopenéconnectionvrstvy
– see Power Point presentations
„Silicon”, „Bipolar technology”
and „MG CMOS” .
Electro-
magnetic
radiation
generators
Electromagnetic Generators
Electro- Light bulbs, generator, utilizing injection
luminofore neon lamps lasers (gas, electroluminescence
solid-state)
Coherent Non-coherent
laser light emitting
semiconductive semiconductive
diodes LD diodes LED
infrared,
visible light
lasers, ultraviolet,
X-ray.
scientific,
measurement,
medical,
technological,
power plant industry,
military.
By the work regime: continuous or pulse lasers.
a) Solid state lasers
Ruby laser – active medium is corundum crystals (Al 2O3) with chromium addition which is the active
compound. Irradiation the crystal by light of sufficient intensity and suitable wavelength, e.g. xenon arc lamp
3+
(pulse duration in the order of tenths of millisecond) results in excitation of chromium Cr ions. An active
environment is created inside the crystal, able to amplify the input beam by stimulated emission. The beam is also
amplified by spontaneous emission. Ruby crystal is placed between two mirrors. The mirrors are parallel and
perpendicular to the crystal axis – photons with trajectory perpendicular to the mirrors are repeatedly reflected. The
light spreading along the crystal axis gets immensely amplified. One of the resonator mirrors is partially transparent
for the generated light and part of the light thus escapes to the surroundings. Ruby laser emits red light and
consumes the light from the arc lamp (shorter wavelengths, green region of spectrum). Elliptic mirrors are used in
modern lasers.
The most common are neodymium lasers , with the neodymium ions Nd 3+ dispersed in yttrium-aluminum
garnet matrix – Nd:YAG for short. Neodymium ions are excited by optic irradiation. Inside them, the photons are
absorbed and emitted in four quantum-level energy system. Laser produces infrared beam of high intensity. YAG
laser is characteristic for its high efficiency; irradiated with simple light bulb can produce continuous light of
hundreds watts intensity. Lately, YAP lasers with yttrium-aluminum perovskite crystal are often utilized. Active
additive is usually rare earth elements, Cr, Co, Ni or U. These elements emit predominantly red and infrared light.
Er:YAG is doped with erbium Er 3+ - produced light of 2. m94 m wavelength has high absorbance in water and
body fluids which is utilized in medicine and dental applications.
b) Liquid lasers
Liquid lasers operate with chelates of various rare earth elements. Most important part of this group is pigment
lasers, employing solutions of various organic compounds, e.g. rhodamine. Color center lasers have crystals with
defects which absorb spectral lines corresponding to various colors (KCl crystal with lithium addition).
c) Gas lasers
The active medium is a gas mixture sealed in a cylindrical tube made of special glass. Its inner diameter is
usually units to tens of mm, its length can be from several cm to couple meters. Gas lasers are perspective and
Light guide
Epoxide
7.1.2 Photo-detectors
Photo-detectors are usually terminal components of the OE system. Almost all photo-detectors in OE circuits
utilize the photoelectric or photovoltaic effect. Free charge carriers are generated during absorption of light in
semiconductor which subsequently increases its electric conductivity , or crystal increases its temperature by
absorption which can also increase the conductivity. Photo-detectors are fabricated as components for selected light
type (wavelength).
Origin of photovoltaic conductivity
a) Transition of carriers from valence band to conduction band if energy of the absorbed light is higher than h > W.
This limit is very distinctive in forward transfer semiconductive materials.
b) Ionization of donor centers. Its low activation energy allows for absorption of light with greater wavelength .
c) The number of free carriers is constant. However the photon energy causes their redistribution on individual
energy levels (excited state) and as a result also changes in their mobility. Externally, change in electric
conductivity is observed.
Photo-detector design
a) Structure of detector with PN junction. Si diode fabricated by common diffusion technology.
b) Silicon PIN diode. On the substrate plate made of high-ohmic – intrinsic Si, N + layer prepared by epitaxy, thin
+
P layer by ionic implementation. On top of these layers, a layer of SiO 2 is produced to reduce the light losses
caused by reflection. PIN diodes are characteristic for their high photo-sensitivity (maximum at = 0.9 m), quick
response and adjustability for integrated circuits.
+
c) Photodiodes with heterogeneous structure. On GaAs plate, N layer is produced by epitaxy from liquid phase
+
and P from solid solution of Ga0,6Al0,4As. This solution has about cca 0.4 eV higher W than N layer of GaAs.
Fiber lighguides
Main application is long-distance information transfer. Their attenuation of the signal is therefore the main
attribute. The absorption of the transferred signal in the material is the most important signal -loss mechanism. This
is caused mainly by Cr, Mn, Fe, Co, Ni, Cu and other compounds. Inhomogeneity, induced to the material during
-
fiber production, can also cause some absorption. Another mechanism is harmonic oscillation of radical group OH
(water in the material). Other important attributes are: mechanical properties - mainly tensile strength, flexibility,
resistance in its environment, lifetime, chemical stability, and small dependence of parameters on temperature and
ionizing radiation. For the purpose of long distance electromagnetic wave transport, only the fiber optic light
guides are of practical importance.
Material requirements and basic fiber light guide types
Fiber light guides are exclusively produced from glass. The active part of the fiber must be from pure high-
quality or doped SiO2 with suitable fiber geometry. The simplest optic waveguide consist of optical fiber from
homogeneous material surrounded by atmosphere.
b)
c)
Fig. 7.4 Three basic types of optical
fiber: configuration geometry (core,
coat, cover), relationship between n
and the fiber diameter r, transport and
Cover distortion of the signal after passing
Core Coat through the waveguide
Coated waveguide has round core made of material with higher refractory index surrounded by coat made of
material with lower refractory index. The refractory index profile is discontinuous on the core- coating interface.
Fig. 7.4 lists examples of typical fiber waveguides and index profiles n of the waveguide with step and gradual
profile in relationship to the fiber diameter r.
Coated waveguides are produced as single - or multi-mode (mode defines the relative position of electrical and
magnetic field intensity vectors). Single mode waveguide have, even with very low refractory index, core diameter
of about 5 m and outer diameter of the cover cca 75 m – Fig. 7.4a). Multi-mode waveguides have core diameter
more than 60 m and outer cover diameter around 75 m – Fig. 7.4b).
Waveguides with gradient change of the refractory index, also known as gradient waveguides - Fig. 7.4c).
Gradient waveguides are fabricated with various refractory index profiles. Commonly, the refractory index profile
is parabolic relatively to the fiber diameter. The index is the highest in the fiber core; the index difference in the
core and on the edge is 0.01 to 0.02. Production technology of these light guides is very complex. However they
have very good transport properties.
Materials for fiber waveguides
Most frequently made of special high-purity glass, quartz, some kinds of plastic or combination of quartz and
plastic. The glass is usually multi-component type, most frequently the sodium-calcium, boron-silicon, phosphate-
silicate or alkali-lead glass. Plastic can either form the whole light guide or just protective coating on the light
guide. Best results were achieved with PMMA (polymethylacrylate). Plastic coatings are usually made of polyvinyl
fluoride or polymethyl siloxane.
aa) method CVD – Fig. 7.5a). Appropriate substances are fed to the rotating quartz tube. Transport medium is
oxygen. The reaction space is heated to the dissociation temperature of gaseous SiCl 4 and GeCl4. Desired Si
and Ge oxides condense on the inner wall of the tube in desired ratio. During the decomposition process, the
high-temperature zone is shifting along the tube to produce homogeneous and uniform layer of Si(Ge)O 2 along
the whole tube. The new layer of Si(Ge)O 2 has higher refractory index than the former SiO 2 tube. Precise
dosing, the uniformity of the heating, rotation and shift of the zone all correspond to the final properties of the
layer.
bb) high-frequency plasma application – Fig. 7.5b). This process takes place at pressures up to 2.5 kPa and lower
temperature – up to 1000 °C.
cc) preform preparation – after the condensation phase, perfectly round rod– preform – is slid inside the tube at
elevated temperature - Fig. 7.6.
N-type silicon
no load voltage U = 0.6 V PN junction
full load voltage = cca 0.5 V P-type silicon
Construction configuration of the photovoltaic cell
Based on the molecule configuration, the liquid crystal phases can be divided into several groups:
A. Nematic phase
Molecules are independent and can move freely in all directions. However elongated molecules are oriented in
certain direction called the director, n . It is so called orientation configuration, typical for liquid crystals.
Molecules rotate freely along both their shorter and longer axis. Molecules in nematic phase flow in all three
directions and their viscosity is close to that of isotropic liquid phase.
C. Smectic phase
There is a single-dimension arrangement of the molecules, as in layered structure. The layers can slide on each
other and flow in one plane. Some smectic phases have multi-dimensions arrangement. The molecules rotate in the
layers so their axis is still in the plane defined by the layer.
D. Columnar phase
The molecules in columnar – discotic phases in shape of discs or plates organize into relatively firm columns
together forming cubic or hexagonal structure. Bond between individual columns is weak, so the columns can glide
freely. Ferroelectric liquid crystals are promising variant of an LCD. Their main difference compared to
nonmagnetic structures is their own, adjustable, polarity. The polarity of single cell or the polarity of whole crystal
can be changed almost permanently by external force. In practice, this means that image on reflex ferroelectric TFT
(thin-film transistor) LCD display will be visible even during power shortage. Their major advantage is their speed
and wide viewing angles.
Liquid crystal materials
These are polyanilin based compounds exhibiting solid phase properties in one dimension and liquid phase
properties in other. Some parts of biomass provide raw material for liquid crystal production. Those are
saccharides, more precisely saccharide surfactants.
[V.m-1]
Spontaneous polarization depends on temperature, frequency and intensity of the external electric field. The
biggest peculiarity of the ferroelectrics is non-linear dependency of the polarization P on electric field intensity E
and existence of electric hysteresis. Characteristic hysteresis loop is shown on Fig. 7.10. It is obvious that at
certain gradient of electric field the material becomes saturated, with all domains oriented in the direction of the
field; further increases of the field intensity has no effect on polarization. The loop is characteristic by saturated
polarization Ps, remanent polarization Pr which is polarization remaining in material after lowering the electric
field intensity to zero and by coercive intensity of electric field Ec, corresponding to the field intensity necessary
for complete depolarization of the ferroelectric ( P = 0). Ferroelectrics remain spontaneously polarized up to certain
temperature, Curie temperature Tc. The Brown motion energy of ions above Tc is so high that it interferes with
aligned ions in neighboring cells and ferroelectric properties of the material disappear.
Barium titanate (BaTiO3) has, above 120 °C, ideal cubic structure of perovskite type – Fig. 7.11. In the center
of the cube, with barium cations in the corners, there is a titanium cation surrounded by six oxygen anions which
are placed in the center of the cube faces. Bellow 120 °C, the elementary cell elongates in direction of one edge and
the structure is changed to tetragonal – ditetragonal pyramidal type. Spontaneous polarization also occurs; its
Fig. 7.12 Thermal dependency of permittivity of BaTiO3 Fig. 7.13 Ferroelectric domain
Substantial flattening can lead to reduction of the maximum permittivity to 1000 - 2000; the permittivity is only
mildly affected by temperature (mild maximum). Application: miniature high-capacity condensers. Big
advantage is that BaTiO3 ferroelectrics can be produced by powder metallurgy. Their greatest asset is simple,
undemanding miniaturization of the circuits. It utilizes high permittivity ( εr = 150 ÷ 15000) for example of
miniature ceramic condenser production. Practical application also utilize the piezoelectric properties of
ferroelectric, e.g. in resonators and in electromagnetic converters (gramophone pickups).
Ferroelectric also exhibit some other interesting properties, such as pyro-electric (temperature dependent
polarization change) or opto-electric properties.
7.5.1 PIEZO-ELECTRICS
PRINCIPLE OF PIEZOELECTRIC EFFECT
Mechanical pressing of piezoelectric crystal by force F deforms the lattice – this results in electric voltage
generation (Fig. 7.15) on deformed facets of the crystal. Piezoelectric effect occurs only on asymmetrical crystals
– e.g. barium-titanium ceramics and quartz. Magnitude and polarity of the voltage correspond to the magnitude and
direction of crystal deformation. Voltage applied on the piezo-crystal results in deformation of the crystal;
alternating voltage manifest as mechanical oscillation of the crystal.
Piezoelectric components are produced by cutting a
plate from quartz crystal with its edges parallel to axis of
the crystal (x – electrical axis, y – mechanical axis, z –
optical axis). Force applied perpendicularly to the
optical axis, electrifies the crystal and a voltage is
generated on planes perpendicular to the electrical axis.
PIEZOELECTRIC MATERIALS
Basic classification:
a) Crystalline piezoelectric materials (single crystals).
b) Polycrystalline piezoelectric materials (piezoelectric ceramics).
c) Organic polymers (piezoelectric polymers).
a) SINGLE CRYSTAL PIEZOELECTRIC MATERIALS
Typical representative of this group is quartz (SiO2), crystallizing in trigonal crystal system. Desired properties
and attribute correspond to the cut orientation. Other affected parameters are their geometrical dimensions, ratio
between them, sizes and position of electrodes and their shape.
Material examples:
lithium niobate LiNbO3,
lithium tantalate LiTaO3,
germanium-bismuth-oxide
Bi12GeO20, triglycine sulfate TGS.
Semiconductive materials:
beryllium oxide BeO,
cadmium sulfate CdS
gallium arsenide GaAs,
gallium phosphide GaP,
zinc oxide ZnO,
zinc sulfide ZnS.
b) POLYCRYSTALLINE CERAMIC MATERIALS (PIEZOELECTRIC CERAMICS)
Relaxation polarization
Occurs mainly in insulators with charged particles, e.g. dipole molecule or ions, gradually become polarized by the
electric field. Relaxation polarization is temperature dependent end energy is dissipated in dielectric.
Dipole relaxation polarization
Occurs in polar gases and liquids consisting of dipole molecules. Dipole orientation in the E direction is
disturbed by thermal motion.
Ionic relaxation polarization
Occurs in dielectrics with irregularly configured ions, e.g. amorphous structures: inorganic glasses and glass
phase ceramics. Polarization of ions in the structure gaps. Exponential time dependency (both the initiation
and abatement). Thermally dependent – the number of polarized ions increases).
Volume polarization
Free charges motion (migration polarization). Occurs in materials with inhomogeneous structure – carriers
accumulate on the interface volume charge.
Interlayer polarization
Occurs in mica and insulators with layer-like structure (cardboard, impregnated paper, relanex, ...).
High-voltage polarization
Occurs in insulators with uni-polar conductivity (ions in inorganic glasses) in strong DC voltage. The strong
voltage causes release of carriers and their movement towards the electrode; layer near the other electrode is
deprived of the carriers unequal charge distribution.
Special polarization
Spontaneous polarization
Occurs in dielectrics with non-organized domain structure (ferroelectrics). The voltage E domain alignment,
spontaneous polarization is thermal dependent: Curie temperature Tc.
Dependency on E : non-linear, dielectric hysteresis, saturation.
Resonance polarization
At very high frequencies (visible spectrum). Frequency comparable to the particle oscillation.
Hydrogen
Gas with the highest thermal conductivity. Used for cooling of large rotary machinery. Its heat transport capacity
is higher than that of air and thus increases efficiency of the device. Drawback is its flammability and that it forms
explosive mixtures with air and also its low dielectric strength. Hydrogen is utilized as filling gas for discharge
lamps and other devices, in electric furnaces as reduction or reaction atmosphere, also as extinguishing agent in
electric switches, as cooling and insulation gas in large rotary machinery (synchronous compensators,
flywheels), as filling gas of some types of vacuum tubes, in semiconductor production and others.
Oxygen
is used in welding as oxidation environment. Air oxygen forms ozone during el. discharges.
Metal vapors
Mercury rectifiers are filled with mercury vapors, sodium arc lamps by sodium vapors.
Mineral oils
Oil properties from the gas solubility perspective – absorbs both water and gases, drawback: aging and
oxidation.
Application: - power oil transformers, oil cables, high- and very-high voltage grommets, switches, capacitors.
Mineral oils are distilled from crude oil. Impurities containing oxygen are removed by refining. Properties of the
oil correspond to its chemical composition.
Transformer oils – utilized in transformers, to keep them at temperatures where they provide favourable
electrical properties. Viscosity and its thermal dependence are crucial. Another important attribute is flash
point, i.e. lowest temperature, at which it can vaporize to forming an flammable mixture with air.
Cable oils – require the viscosity to be low after impregnation of the cable – the oil can therefore fill the cavities
and saturate porous insulation (e.g. paper). Pure oil is not used for impregnation purposes – it is usually mixed
with resin, forming oil compounds. The resin reduces the flow-down and prolongs the service life of
insulation. Utilized mostly in switches to quickly extinguish the arc discharge which occurs during contact
separation.
Capacitor oil – requires higher stability.
Synthetic liquids – excellent insulation and dielectric properties. Non- flammable, non-explosive, highly stable
and practically do not age. Esther based liquids represent large portion of the synthetic liquids. Chemically
stable, withstands higher temperatures with excellent dielectric properties. Application: - filling or
impregnation for cables, film capacitors and others.
Chlorinated biphenyles, e.g. pentachlorbiphenyle. Harmful.
Fluorinated hydrocarbons, non-polar and excellent dielectric properties.
Electrolytes – liquids or sometimes solids, el. conductive. Solutions of molecules formed by reaction of two
opposite polarity ions. Current conduction causes transport of mass from anode to cathode. This is utilized in
galvanic metal coating, electrolysis (decomposition by electric current), galvanic cell – both primary and
secondary and in electrolytic capacitor.
Varnish is a solution of film-forming compounds (natural or synthetic resin, drying plant oils and asphalt) in
organic thinner. Varnishes are divided in groups by their chemical composition:
- natural resin,
- alcohol varnish,
- drying oil – oil varnish,
- synthetic resin – synthetic varnish.
Classification
Drying oil varnish – protection against exterior influences.
Phenol formaldehyde varnish – saturation of coil wiring.
MICA
Crystalline mineral which, thanks to its layered structure, easily chips to form very thin leaves. Stable even at
high temperatures and in many chemical substances. Mica is characterized by having very good dielectric and
chipping properties, elasticity, and high thermal resistance. Mica is found in nature in many kinds however only
several are utilized for technical applications:
MUSCOVITE - potash mica
PHLOGOPITE – magnesium mica
Crude mica is suitable for pads for electric heated and regulation resistors. Chopped mica (thickness of 0.05
to 0.45 mm) is utilized for production of multi -layered insulators MICANITE, MICACOIL and MICA STRIPS.
Mica exhibits low dielectric losses; dielectric strength depends on the thickness of layer. The dielectric strength
increases with decreasing layer thickness. Dielectric strength of muscovite is higher than that of phlogopite.
Maximum operation temperature of muscovite is 600 °C, resp. 900 °C for phlogopite.
Mica waste processing technology produces elastic, electro-insulation material in form of a foil called
REMICA – mica waste and least valuable ore constituents are processed – production of multilayered insulators.
Application of mica in electrical engineering:
- dielectrics in capacitors, material for insulation desks (micanite, mica folium), strips, electrode bearing
systems and heating wires,
- milled mica with low-melting glass is utilized for pressed insulation (micalex). It is also utilized in HF
technology at high temperatures. It has excellent properties for use in electrical engineering, including HF
and vacuum technology.
- micanite with bonding agent is used for production of commutators; board- or foil-shaped mica is used for
production of heating wires (micafolium and mica strip).
MICANITES are fabricated from mica strips glued together by a bonding agent (shellac, epoxide) on a substrate –
typically fibre glass, paper.
Hard micanite (commutator) – insulation of commutator lamels.
Elastic micanite – partially hardened bonding agent – commutator cuffs, slot insulation.
MICAFOLIUM two layers of strips on elastic substrate, sticky surface – wrapping and ironing of high-voltage
coil insulation.
MICALEX – milled mica waste with glass bonding agent – construction and insulating material.
CERAMIC MATERIALS
Ceramic typically has good electro-insulation properties, its properties are time-stable and it has good resistance
against high-temperature, temperature-shock, chemicals, exterior conditions and humidity. Ceramic has very high
hardness, and is usually brittle. Its compressive strength is usually one order of magnitude higher than its tensile
strength. Considering the constriction caused by firing, it is difficult to produce dimension-precise products
without further working - grinding.
Kaolin and clay are the raw materials for production of silicate ceramics such as pottery, earthenware and
mullite ceramics. e.
Chemical composition: - silicate ceramics: SiO2 + mixture of metal oxides,
- non silicate ceramics: TiO2, BaTiO3,
- oxide ceramics: Al2O3, MgO, BeO,
- non oxide ceramics: hard and resilient (carbides, nitrides, silicides etc.).
G L A S S is amorphous inorganic material (super- cooled liquid). Ions of additives (Na+, K+, and others.) modify
various properties of glasses such as melting point, strength, brittleness, colour and electrical properties.
Technical glass belongs to the group of materials which do not solidify at specific temperature due to
crystallization like metals, rather can be super-cooled bellow this point. Favourable attributes of technical glass is
good hot formability, good electrical, thermal and chemical properties, that it is impervious for gasses and
can form vacuum tight seals with metal.
Physical properties of glass
Temperature dependency of viscosity corresponds to the production technology and subsequent working of
the glass.
Considerable thermal and chemical resistance.
Optic properties – refractory index, reflection.
Vacuum tight.
Mechanical properties of glasses correspond to the state of the surface and also temperature (expansivity).
Glass is brittle, can better withstand pressure than tensile stress.
Glass fibres have high tensile strength.
Electric properties of glass
Depends on chemical composition and operation conditions. Ionic type electric conductivity. Dielectric
strength of glass is, compared to other insulators, high: Ep ~ 200 400 kV·cm-1, however it is much lower in
practice. Glass is strongly polar, r = 3.7 (pure quartz glass) to r = 16.5 (lead glass) or even more.
Types of glass and their application
In electrical engineering, glass is mostly used for insulation and construction purposes, e.g. light bulbs,
discharge lamps, fluorescent tubes, vacuum tubes, displays and other vessel shapes for electrodes kept in
vacuum, gases or vapors.
Quartz glass low losses – 99.9 % SiO2, transparent or opaque, good thermal properties.
Application: coil frames for HF technology, vessels and cases for discharge lamps and rectifiers.
Boron-silicate glass (hard glass) – many kinds with good electric properties (SIMAX) – utilized in HF
electrical engineering, tungsten, molybdenum and covar seals. Suitable for optic fibre production for light
guides, production of PCB (printed board circuit) by joining glass fabric by epoxide, silicon, in
microelectronics (substrate for thin layers) and others.
Lead glass (soft glass) – receiver vacuum tubes, necks of TV screen tubes.
Alkali glass (MgO) – easy meltable, can not withstand rapid temperature changes - lighting, screens,
insulation (fabrics, lamination, glass insulators).
Special glass – hardened, sintered, electric conductive glass (cermet potentiometers), magnetic glass, for vapor
deposition from vacuum, conductive glass, glass solder.
Glass fibre fabricated from Eutal by drawing a wire from melt liquid in Pt crucible, diameter ~ 5 10 m, 100
200 fibres. Fibres are then processed to produce thread, cord or fabric.
ORGANIC INSULATORS . For example both natural and synthetic oil, wax, asphalt, drying oil, natural resin,
natural rubber, plastics, varnish, fibrous and layered insulator.
Organic insulators are, in most cases, essentially macromolecular compounds; building units (monomers) are
connected in periodic manner to form macromolecule (polymer) . Chemical structure of the macromolecule
determines its electrical, mechanical and chemical properties, as well as their thermal resistance. The configuration
of monomer molecules in macromolecule can be:
- linear.
- branched,
- spatial.
3. VARNISH
2. THERMOPLASTICS
This is a group of plastics which, subjected to heat, soften; they recover their former properties when cooled.
Exceeding the fusion temperature results in decomposition of thermoplastic material. Their dielectric properties at
various frequencies, temperatures and humidity levels must be measured, if they are utilized for electrical
engineering purposes.
POLYSTYRENE (PS) is amorphous, glass-like material. It is non-polar, its molecules have small dipole moment.
It relatively good light conductor, it has low thermal resistance (-30 to +70 °C), and starts softening already at
85 °C. Polystyrene is used for production of injected mouldings (e.g. device covers). Polystyrene is typical
insulator for high-frequency purposes. It is used also for coaxial cable jacks, various construction components
of measurement devices and others.
Oriented polystyrene film (Styroflex) - dielectrics of foil capacitors or insulation of HF cables.
Foam polystyrene materials - casings (eventually casing fillers) for appliances.
POLY(METHYL METHACRYLATE): polyester of acrylic acid, transparent for UV light– DENTACRYLE (brand
name), material for moulds.
POLYAMIDE – conductor insulation in dry environment. Fibres (SILON, NYLON). Application: cogwheels, ball
bearings, crystalline thermoplastics.
POLYFORMALDEHYDE chemically resistant, welded joints. Application: cogwheels in HF applications, flexible
pens, flat springs.
3. ELASTOMERS
Substantial part of insulation of all conductors. Basic attribute of all elastomers is their high flexibility. They can
be, at room temperature and reasonable load, elongated to double their length; they quickly return to its original
dimensions if the stress is relieved. Vulcanization of elastomers enhances their properties. Most important
elastomers are natural rubber and rubber. Utilized as seals, insulation grommets, dampening components and
construction parts, eventually as potting material for electronic circuits.
RUBBER
Rubber can be vulcanized by addition of sulphur or sulphur compounds. This enhances its tensile strength,
flexibility and also thermal, chemical and mechanical resistance. However, rubbers easily oxidize, e.g. by ozone
which results in quick deterioration of mechanical properties – aging.
Natural rubber is produced from latex of some tropical trees (Hevea brasiliensis). Ultraviolet light causes
quick aging of rubber, facilitated by photochemical oxidation. Rubber rapidly loses its elasticity and becomes
insoluble and brittle. Elastic gum is produced by mixing and vulcanization of rubber. Elastic gum is used for
production of cable insulation, its drawback is low thermal resistance.
Synthetic rubber produced from acetylene, benzene other compounds from crude oil, natural gas or coal.
Butadiene rubber – thermal vulcanization at 200 °C without sulphur. Application: - cable insulation.
Styrene-butadiene rubber - elastic, chill-resistant. Application: insulation of cables, conductors (increased
resistance at low temperatures).
Chloroprene rubber – strongly stressed insulation.
Silicon rubbery: good el. properties, high thermal resistance (up to 180 °C), chemical stability, hydrophobic.
Application: insulation of thermally-stressed cables, capacitor and transformer potting material.
- ceramic,
- mica multilayered,
- electrolytic,
- tantalum.
Ceramic capacitor
This is the type of capacitor most widely used in electronic devices. High stability of ceramic capacitors is
mainly caused by heterogeneity of ceramics. Dielectric constant of these components is around r = 10 (pure
aluminum oxide Al2O3) up to r > 10000 (e.g. BaTiO3).
Ceramic capacitors are mostly utilized in HF engineering. The dielectric is usually titanium, zirconium or tin
oxides, in technical practice called STABILITE, STEATITE, RUTILITE and PERMITITE. These capacitors
have high capacity and miniature dimensions.
Most common types of ceramic capacitors:
disc capacitors,
desk soldered directly to copper conductor,
flat,
tube,
grommet comprising of ceramic tube.
Super-capacitor also called Gold cap , is special small capacitor with capacity of 0.1 F to 1 F. This high value is
achieved by implementation of special porous electrodes. Cannot be charged or discharged by strong currents since
current stronger than few mA damages the capacitor. Fabricated typically for voltage around 5 V. These capacitors
replace NiCd accumulators utilized as source for CMOS components.
Varicap
Varicaps are one kind of adjustable, semiconductor based capacitator. Utilized in tuning circuits, automated
frequency circuits, in modulation circuits for frequency modulated transmitters and others. They utilize the
fact that each PN junction has certain capacity which changes with polarization voltage put on the junction
terminals. Commonly available varicap types have capacity of 2 to 15 pF (types for very-high-frequency circuits)
or 12 to 250 pF (tuning circuits up to 30 MHz) for voltage changes between 1 to 30 V.
BOUDA, V., HAMPL, J., LIPTÁK, J.: Materials for Electronics. University mimeographed, ČVUT Prague, 2000.
HARPER, Ch.A.: Electronic Materials and Processes Handbook. McGraw-Hill, 2004.
KLAUK HAGEN: Organic Electronics: Materials, Munufacturing and Applications. Willey-VCH, 2006.
DORF, R.C.: The Electrical Engineering Handbook Series. Second Edition. CRC Press, 2005.
WHITAKER, J.C.: Microelectronics. Second Edition. CRC Press, 2006.
DRÁPALA, J., KUCHAŘ, L.: Metallurgy of Pure Metals. Cambridge International Science Publishing Ltd, 2008.